WO2021210386A1 - Latent heat storage material-integrated active carbon and production method thereof - Google Patents

Latent heat storage material-integrated active carbon and production method thereof Download PDF

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WO2021210386A1
WO2021210386A1 PCT/JP2021/013531 JP2021013531W WO2021210386A1 WO 2021210386 A1 WO2021210386 A1 WO 2021210386A1 JP 2021013531 W JP2021013531 W JP 2021013531W WO 2021210386 A1 WO2021210386 A1 WO 2021210386A1
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latent heat
heat storage
storage material
activated carbon
integrated
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PCT/JP2021/013531
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French (fr)
Japanese (ja)
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邦寿 岩崎
建司 関
一樹 坂井
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大阪ガスケミカル株式会社
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Priority to JP2022515283A priority Critical patent/JPWO2021210386A1/ja
Publication of WO2021210386A1 publication Critical patent/WO2021210386A1/en

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
    • B01D53/04—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography with stationary adsorbents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F02—COMBUSTION ENGINES; HOT-GAS OR COMBUSTION-PRODUCT ENGINE PLANTS
    • F02M—SUPPLYING COMBUSTION ENGINES IN GENERAL WITH COMBUSTIBLE MIXTURES OR CONSTITUENTS THEREOF
    • F02M25/00—Engine-pertinent apparatus for adding non-fuel substances or small quantities of secondary fuel to combustion-air, main fuel or fuel-air mixture
    • F02M25/08—Engine-pertinent apparatus for adding non-fuel substances or small quantities of secondary fuel to combustion-air, main fuel or fuel-air mixture adding fuel vapours drawn from engine fuel reservoir

Definitions

  • the present invention relates to an activated carbon integrated with a latent heat storage material and a method for producing the same.
  • the organic solvent recovery system that liquefies and recovers the organic solvent has advantages that the amount of carbon dioxide emitted is smaller than that of the combustion device that burns and detoxifies the organic solvent, and that the recovered organic solvent can be reused.
  • the organic solvent recovery system executes an adsorption step of adsorbing and removing the organic solvent in the gas to be treated with the adsorbent and a desorption step of desorbing the organic solvent adsorbed on the adsorbent by an inert gas such as heated air. It is configured by providing a switching means or a means for continuously performing the adsorption step and the desorption step alternately in time.
  • Exhaust gas emitted to the atmosphere by automobiles which is one of the sources of air pollutants, includes exhaust gas from fuel burned by an engine, hoisting dust that tires wind up while driving, fuel mounted on automobiles, and solvents for automobile materials. There is exhaust gas etc. generated from such as.
  • the canister which is an automobile part, temporarily adsorbs (collects) the gasoline vapor evaporated in the fuel tank to the activated carbon and suppresses the discharge to the outside of the vehicle.
  • the vapor temporarily adsorbed (collected) on the activated carbon is purged (scavenged) by using the negative pressure of the intake pipe of the engine during running, and is configured so that the performance can be maintained repeatedly by burning the engine. ..
  • the adsorbent is required to have high-quality adsorption / desorption performance, but the adsorbent itself has the property that the lower the temperature, the higher the adsorption capacity, and the higher the temperature, the higher the desorption ability.
  • One of the important factors when sought is temperature.
  • the heat that goes in and out of the adsorbent when various gases, liquids, vapors, etc. are attached to and detached from the adsorbent is controlled by flowing a medium such as water from the outside, or a substance with high thermal conductivity is inserted. Although it is possible to suppress the temperature rise by mixing substances with high heat capacity, the equipment becomes heavier and larger.
  • Patent Documents 1 and 2 describe a latent heat storage type adsorbent for canisters, which includes an adsorbent that adsorbs vaporized fuel and a latent heat storage material in which a phase change substance that absorbs and releases latent heat depending on the temperature is encapsulated in microcapsules. Proposed. According to this adsorbent, the adsorption-desorption performance of the transpired fuel is significantly superior to that of the conventional one due to the temperature control during adsorption and desorption, so there is an advantage that a small and high-performance adsorption tower and canister can be supplied. There is.
  • Durability against solvent vapor is important to maintain high level of adsorption / desorption performance for a long period of time.
  • the surface of the latent heat storage material is physically damaged, and when exposed to VOC steam, the latent heat substance in the microcapsules constituting the latent heat storage material leaks out. Therefore, the original performance of the adsorbent cannot be brought out due to the decrease in the amount of heat of the latent heat storage material and the blockage of the pores of the activated charcoal.
  • an object of the present invention is to integrate the latent heat storage material and the activated carbon while suppressing damage to the latent heat storage material, rather than simply mixing the latent heat storage material and the pellets of the activated carbon. It is an object of the present invention to provide an adsorbent which can prevent heat transfer loss in intergranular voids and can maintain a high level of adsorption / desorption performance and durability by effectively controlling the heat of adsorption.
  • the present inventors coated the surface of the microcapsules containing the phase-changing substance with an organic binder-containing layer containing a thermosetting organic binder A, and further. It has been found that by coating with an activated carbon-containing layer containing activated carbon, an adsorbent capable of maintaining a high level of adsorption / desorption performance and durability can be obtained. Based on such findings, the present inventors have further studied and completed the present invention. That is, the present invention includes the following configurations.
  • a latent heat storage material integrated activated carbon containing microcapsules containing a phase-changing substance that absorbs and releases latent heat depending on the temperature and activated carbon In the latent heat storage material, the surface of the microcapsules is coated with an organic binder-containing layer containing a thermosetting organic binder A, and the latent heat storage material is coated with an organic binder-containing layer.
  • Item 2 The latent heat storage material integrated activated carbon according to Item 1, wherein the microcapsules have an average particle size of 0.1 to 500 ⁇ m.
  • Item 3 The latent heat storage material integrated activated carbon according to Item 1 or 2, wherein the activated carbon has an average particle size of 1 ⁇ m to 10 mm.
  • Item 4. The latent heat storage material integrated activated carbon according to any one of Items 1 to 3, wherein the activated carbon-containing layer further contains an organic binder B.
  • Item 5 The latent heat storage material integrated activated carbon according to any one of Items 1 to 4, wherein the pH of the aqueous suspension of the activated carbon-containing layer measured in accordance with JIS K 1474 (2014) is 4.5 or more. ..
  • Item 6 The latent heat storage material integrated activated carbon according to any one of Items 1 to 5, wherein the latent heat storage material has an average cross-sectional diameter of 0.75 to 1.80 mm.
  • Item 7 The latent heat storage material integrated activated carbon according to any one of Items 1 to 6, wherein the content of the latent heat storage material is 7 to 30% by mass, where the total amount of the latent heat storage material integrated activated carbon is 100% by mass. ..
  • Item 8 The latent heat storage material integrated activated carbon according to any one of Items 1 to 7, which has a calorific value of 10 to 100 J / g.
  • Item 9 The latent heat storage material integrated activated carbon according to any one of Items 1 to 8, which has an ASTM hardness of 45% or more.
  • Item 10 The method for producing a latent heat storage material-integrated activated carbon according to any one of Items 1 to 9.
  • Step of mixing the microcapsules and the thermosetting organic binder A (2) The microcapsule composition obtained in step (1) is coated with the thermosetting organic binder A and heat-treated to obtain the above.
  • the process of obtaining latent heat storage material (3) A production method comprising a step of mixing and granulating the latent heat storage material obtained in the step (2) and the composition containing the activated carbon.
  • Item 11 The production method according to Item 10, wherein the step (1) is a step of mixing the microcapsules and the thermosetting organic binder A, then extruding and granulating, and then sizing.
  • Item 12 The production method according to Item 10 or 11, wherein in the step (3), the composition containing the activated carbon further contains the organic binder B.
  • Item 13 The production method according to any one of Items 10 to 12, wherein in the step (3), the composition containing the activated carbon further contains a pH adjuster.
  • Item 14 An automobile canister containing the latent heat storage material integrated activated carbon according to any one of Items 1 to 9.
  • Item 15 An automobile canister connected to a closed gasoline tank containing the latent heat storage material integrated activated carbon according to any one of Items 1 to 9.
  • an activated carbon with a latent heat storage material that can maintain a high level of adsorption / desorption performance and durability.
  • the latent heat storage material integrated activated charcoal of the present invention contains a latent heat storage material having microcapsules encapsulating a phase change substance that absorbs and releases latent heat depending on the temperature, and an activated charcoal.
  • the surface of the microcapsule is coated with an organic binder-containing layer containing a thermosetting organic binder A, and the surface of the latent heat storage material contains activated charcoal. It is coated with an activated charcoal-containing layer.
  • the latent heat storage material integrated activated charcoal having such a configuration can be produced without physical damage to the latent heat storage material, elution of inclusions from the latent heat storage material is suppressed when exposed to a solvent. It is stable for a long period of time, and its structure is such that the surface of one latent heat storage material is coated with activated charcoal, and the temperature rise due to heat of adsorption can be efficiently suppressed by the latent heat storage material, so that it exhibits high solvent absorption / desorption performance.
  • phase-changing substance encapsulated in the microcapsules is not particularly limited as long as it is a compound capable of absorbing and releasing latent heat as the phase changes.
  • phase change for example, a phase change between a solid and a liquid can be exemplified.
  • the temperature at which the phase-changing substance can undergo a phase change (for example, melting point, freezing point, etc.) can be appropriately selected depending on the use of the canister, but is usually about 0 to 50 ° C.
  • phase change material preferred compounds, for example, tetradecane, pentadecane, hexadecane, heptadecane, octadecane, nonadecane, eicosane, aliphatic hydrocarbon straight, such as docosane, natural wax; petroleum waxes; LiNO 3 ⁇ 3H Hydrate of inorganic compounds such as 2 O, Na 2 SO 4 ⁇ 10H 2 O, Na 2 HPO 4 ⁇ 12H 2 O; Fatty acids such as capric acid and lauric acid; Higher alcohols having 12 to 15 carbon atoms; Palmitic acid Examples thereof include ester compounds such as methyl and methyl stearate.
  • the phase change substance can be used alone or in combination of two or more for the purpose of adjusting the melting point.
  • a combination is preferable in which the difference in temperature at which the phase-changing substances of each phase-changing substance occurs is about 0 to 15 ° C.
  • a compound having a melting point higher than the melting point of the phase-changing substance in order to prevent the supercooling phenomenon of the phase-changing substance, a compound having a melting point higher than the melting point of the phase-changing substance can be contained.
  • refractory compound examples include aromatic compounds, esters, carboxylic acids, alcohols, amides and the like.
  • the refractory compound may be used alone or in combination of two or more.
  • Examples of the aromatic compound include halogen-substituted benzene and naphthalene.
  • the halogen-substituted benzene include dihalogenated benzene such as dibromobenzene and dichlorobenzene.
  • esters examples include fatty acid esters of monoalcohols such as methyleicosanoic acid; fatty acid esters of glycerin such as linoleic acid glyceride.
  • carboxylic acids examples include aliphatic carboxylic acids such as myristic acid, pentadecylic acid, palmitic acid, margaric acid, stearic acid, nonadesyl acid, eicosanoic acid, henicosanoic acid and bechenic acid; and aromatic carboxylic acids such as benzoic acid. It can be exemplified.
  • alcohols include monoalcohols having 16 to 30 carbon atoms such as cetyl alcohol, heptadecanol, stearyl alcohol, nonadecanol, and eikosanol.
  • amides include fatty acid amides such as icosane acid amide, nonadecylic acid amide, stearic acid amide, and oleic acid amide.
  • the content thereof is preferably 0.5 to 30 parts by mass and 1 to 15 parts by mass with respect to 100 parts by mass of the content of the phase change substance from the viewpoint of solvent adsorption / desorption performance. More preferred.
  • a known material can be used, and for example, a polymer compound such as a resin can be exemplified.
  • the polymer compound include formaldehyde-melamine resin, melamine resin, formaldehyde-urea resin, urea resin, urea-formaldehyde-polyacrylic acid copolymer, polystyrene, polyvinyl acetate, polyacrylonitrile, polyethylene, polybutyl methacrylate, gelatin and the like.
  • These materials can be used alone or in combination of two or more.
  • the weight ratio of the microcapsule material to the phase-changing substance is not particularly limited, but the total amount of the microcapsule material and the phase-changing substance is 100% by mass, and from the viewpoint of solvent adsorption / desorption performance, the material of the microcapsule is usually used.
  • the content of the phase changing substance can be 10 to 30% by mass, and the content of the phase changing substance can be 70 to 90% by mass.
  • a high melting point compound is used, the total amount of the microcapsule material, the phase change substance, and the high melting point compound is set to 100% by mass, and the content of the microcapsule material is usually set from the viewpoint of solvent adsorption / desorption performance. It can be 10 to 30% by mass, and the total content of the phase change substance and the refractory compound can be 70 to 90% by mass.
  • the method for microencapsulating the phase-changing substance used in the present invention existing techniques such as a core selvation method, an interfacial polymerization method, an in-situ method, and a method using yeast can be used, and any of the methods can be used. However, the effect of the present invention can be achieved.
  • a phase change substance (and a refractory compound if necessary) is emulsified in a liquid medium using an emulsifier or the like, an initial condensate (prepolymer) corresponding to the desired resin is added thereto, and then the temperature is raised. Then, by advancing the polymerization reaction, a microcapsule dispersion (slurry) having a resin wall and containing a phase change substance (and a refractory compound if necessary) can be prepared.
  • Water is particularly preferable as the liquid medium, but alcohols such as methanol, ethanol and propanol, and water-miscible solvents such as acetone can also be used.
  • the above solvent may be used alone or in combination of two or more.
  • the shape of the microcapsules is usually spherical particles (powder or granules), and the particle size of the particles is controlled by the type and concentration of the emulsifier at the time of encapsulation, the temperature and time at the time of emulsification, the emulsification method, etc. Since it varies depending on the factors of, the optimum conditions can be set by experiments.
  • the average particle size of the microcapsules is preferably about 0.1 to 500 ⁇ m, more preferably about 1 to 100 ⁇ m, and even more preferably about 2 to 10 ⁇ m.
  • the average particle size of the microcapsules was measured by a laser diffraction type particle size distribution measuring device (manufactured by Microtrac Bell: Microtrac MT3300EXII), and the particle size when the cumulative volume of the volume standard was 50% was taken as the average particle size.
  • the measurement sample shall be obtained by irradiating 30 min of ultrasonic waves to crush the secondary particles into primary particles.
  • the surface of the above-mentioned microcapsules is coated with an organic binder-containing layer containing a thermosetting organic binder A.
  • the number of microcapsules coated with the organic binder-containing layer containing the thermosetting organic binder A is not particularly limited, and may be one or a plurality (for example, 2 to 10). According to the production method, one microcapsule is usually coated with an organic binder-containing layer containing a thermosetting organic binder A.
  • thermosetting organic binder A a general one can be used and is not particularly limited.
  • a thermosetting resin such as a phenol resin, an acrylic resin, an epoxy resin, an isocyanate resin, a melamine resin, a urethane resin, or an amide ester resin is used.
  • a thermosetting resin in which the JIS hardness (JIS K1474 (2014)) of the obtained latent heat storage material tends to be high is preferable.
  • the thermosetting organic binder A is preferably a resin having high solvent resistance (water resistance, organic solvent resistance, etc.) after molding.
  • the latent heat storage material can easily prevent the dispersion and swelling of the microcapsules by the solvent that can be used in the production method described later, and the latent heat storage material is hard. Easy to maintain. Further, since the hardness of the latent heat storage material tends to be high, it is easy to suppress the pulverization of the latent heat storage material at the time of molding, and it is easy to suppress the destruction of powdered microcapsules by activated carbon.
  • the content of the thermosetting organic binder A in the latent heat storage material easily suppresses the temperature rise due to the heat of adsorption of the activated charcoal, easily improves the amount of latent heat, improves the adsorption performance, and also improves the durability. From the viewpoint of ease, 5 to 20 parts by mass is preferable, 8 to 18.5 parts by mass is more preferable, and 14.5 to 18.5 parts by mass is further preferable with respect to 100 parts by mass of the microcapsule containing the phase change substance.
  • the organic binder-containing layer containing the thermosetting organic binder A may be composed of only the above-mentioned thermosetting organic binder A, or may be a curing accelerator, a coloring agent, a plasticizing agent, a stabilizer, and a release agent.
  • Additives such as a mold agent (metal soap such as zinc stearate) may be contained.
  • the content of such an additive is preferably in a range that does not impair the effects of the present invention, and is preferably 0 to 10% by mass, preferably 0 to 5% by mass, with the total amount of the organic binder-containing layer being 100% by mass. More preferably, 0 to 3% by mass is further preferable.
  • the shape of the latent heat storage material including the organic binder-containing layer is not particularly limited, and any of pellet shape (cylindrical shape, spherical shape, etc.), disk shape, block shape, etc. can be adopted.
  • the average cross-sectional diameter of the latent heat storage material including the organic binder-containing layer is not particularly limited, but it is easy to suppress the temperature rise due to the adsorption heat of the activated carbon, and it is easy to improve the latent heat amount to improve the adsorption performance. From the viewpoint of easy improvement and easy improvement of durability, 0.75 to 1.80 mm is preferable, 0.78 to 1.50 mm is more preferable, and 0.80 to 1.20 mm is further preferable. When passing through a hole such as a die of a molding machine, it is preferable to make the hole smaller than the hole because it is easy to suppress performance deterioration due to cracking of the microcapsules.
  • the average cross-sectional diameter of the latent heat storage material is calculated by calipers.
  • the JIS hardness of the latent heat storage material-integrated activated carbon in the latent heat storage material-integrated activated carbon is from the viewpoint of easily suppressing cracking and pulverization due to contact between the latent heat storage material and the activated carbon, the latent heat storage material-integrated activated carbon of the present invention. Is preferably larger than.
  • the JIS hardness of the latent heat storage material is, for example, preferably 90% or more, and more preferably 95 to 100%.
  • the JIS hardness of the latent heat storage material is measured according to JIS K1474 (2014).
  • the surface of the latent heat storage material having an organic binder-containing layer formed on the surface of the above-mentioned microcapsules further contains activated carbon containing activated carbon. It is covered with a layer.
  • the number of latent heat storage materials coated with the activated carbon-containing layer containing activated carbon is not particularly limited and may be one or a plurality (for example, 2 to 10), but according to the production method of the present invention described later.
  • one latent heat storage material is often coated with an activated carbon-containing layer containing activated carbon.
  • activated carbon used in the present invention a commonly used activated carbon for canisters can be used.
  • activated carbon those obtained from various raw materials such as coal-based, coconut shell-based, wood-based, and lignin-based can be used, and steam activated products; carbon dioxide gas activated products; chemical activated products using phosphoric acid, zinc chloride, alkali metals, etc. Activated carbon products can be used.
  • the activated carbon applied to the present invention may be in any form such as powder, granular, crushed charcoal, etc., but when used for canister applications, it is preferably in the form of powder having pores in order to increase the adsorption capacity of the evaporated fuel. ..
  • the average particle size of the activated carbon powder is not particularly limited, but it is easy to suppress the temperature rise due to the adsorption heat of the activated carbon, it is easy to improve the latent heat amount, it is easy to improve the adsorption performance, and the durability is also improved. From the viewpoint of easy acclimation, 1 ⁇ m to 10 mm is preferable, 5 ⁇ m to 1 mm is more preferable, and 10 to 100 ⁇ m is further preferable.
  • the average particle size of the activated carbon powder is measured by a laser diffraction type particle size distribution measuring device (Microtrac Bell: Microtrac MT3300EXII), and the average particle size is defined as a volume-based cumulative particle size of 50%.
  • the specific surface area of the activated carbon is not particularly limited, but it is easy to suppress the temperature rise due to the heat of adsorption of the activated carbon, it is easy to improve the latent heat amount, it is easy to improve the adsorption performance, and it is easy to improve the durability. From the viewpoint, 500 to 2500 m 2 / g is preferable, 600 to 2400 m 2 / g is more preferable, and 800 to 2000 m 2 / g is further preferable.
  • the specific surface area of activated carbon having a diameter of 30 nm or less is measured by a specific surface area / pore distribution measuring device (manufactured by Microtrac Bell Co., Ltd .: Belsorb miniII), and a nitrogen adsorption isotherm of activated carbon at liquid nitrogen temperature is created. Then, it is calculated by the Cranston-Inkley (CI) method.
  • CI Cranston-Inkley
  • the pore volume of the activated carbon is not particularly limited, and from the viewpoint that it is easy to suppress the temperature rise due to the adsorption heat of the activated carbon, it is easy to improve the latent heat amount, it is easy to improve the adsorption performance, and it is easy to improve the durability, for example, 0.10. It is preferably ⁇ 1.00 mL / g, more preferably 0.20 to 0.90 mL / g, and even more preferably 0.30 to 0.80 mL / g.
  • the pore volume of activated carbon with a diameter of 30 nm or less is measured by a specific surface area / pore distribution measuring device (manufactured by Microtrac Bell Co., Ltd .: Belsolp miniII), and the nitrogen adsorption isotherm of activated carbon at liquid nitrogen temperature is measured. It is prepared and calculated by the Cranston-Inkley (CI) method.
  • the pH of the activated carbon is, for example, a carboxylate state under neutral or basic conditions, and the binder is easily dissolved in water. Therefore, the uniformity of the binder on the surface of the activated carbon is easily improved, and the hardness is improved.
  • the pH of the aqueous suspension of activated carbon measured in accordance with JIS K 1474 (2014) is preferably 4.0 or higher, more preferably 4.5 or higher. 5.0 or more is more preferable.
  • the upper limit of the pH of the aqueous suspension of activated carbon measured in accordance with JIS K 1474 (2014) is not particularly limited, but is usually about 14.0.
  • the content of the latent heat storage material in the latent heat storage material integrated activated coal is from the viewpoint that the amount of temperature change is easily suppressed, the latent heat amount is easily improved, the adsorption performance is easily improved, and the durability is also easily improved.
  • the total amount of the latent heat storage material integrated activated charcoal is 100% by mass, it is preferably 7 to 30% by mass, more preferably 9 to 29% by mass, still more preferably 14 to 19% by mass.
  • the content of activated carbon in the activated carbon integrated with the latent heat storage material is easy to suppress the amount of temperature change, easily improve the latent heat amount, improve the adsorption performance, and easily improve the durability.
  • the total amount of the material-integrated activated carbon as 100% by mass, 62 to 86% by mass is preferable, 63 to 84% by mass is more preferable, and 73 to 79% by mass is further preferable.
  • the activated carbon-containing layer contained in the activated carbon integrated with the latent heat storage material of the present invention may be composed of only the above-mentioned activated carbon, but may further contain an organic binder B.
  • a binder of a thermoplastic resin or a thermosetting resin generally used for molding an adsorbent such as activated charcoal can be used, as well as a paint / adhesive, a fiber treatment binder, and the like.
  • Cross-linking / adhesion improving agents, thermoplastic resins, and additives for coating agents such as films can be used.
  • commonly used ones such as cellulose derivatives such as methyl cellulose and carboxylmethyl cellulose, phenol resins, melamine resins, epoxy resins, urethane resins, polyvinyl alcohols, vinyl acetate, vinylidene chloride resins, and oxazoline-containing polymers can be used without limitation.
  • These organic binders B can be used alone or in combination of two or more. Further, the same one as the above-mentioned thermosetting organic binder A may be used, or a different one may be used.
  • the content of the organic binder B in the activated carbon integrated with the latent heat storage material makes it difficult to block the pores of the activated carbon, easily suppresses the amount of temperature change, easily improves the latent heat amount, and easily improves the adsorption performance and is durable.
  • the total amount of the latent heat storage material integrated activated carbon is 100% by mass, preferably 5 to 10% by mass, more preferably 6 to 9% by mass, still more preferably 7 to 8% by mass.
  • the activated carbon-containing layer contained in the activated carbon integrated with the latent heat storage material of the present invention may be composed of only the above-mentioned activated carbon and, if necessary, the organic binder B. As described above, under neutral or basic conditions, the uniformity of the binder on the surface of the activated carbon is easily improved and the hardness is easily improved, so that the pH can be adjusted with a pH adjuster.
  • Acid, base, salt, buffer solution, etc. can be used as the pH adjuster.
  • bases such as sodium hydroxide, potassium hydroxide, potassium hydroxide, barium hydroxide, ammonia, magnesium hydroxide, calcium hydroxide, aluminum hydroxide; hydrochloric acid, nitrate, phosphoric acid, boric acid, acetic acid, citric acid, Acids such as carbonic acid; salts such as sodium hydrogen carbonate, sodium carbonate, sodium acetate, sodium dihydrogen phosphate, sodium hydrogen phosphate, sodium hydrogen sulfate and the like; buffer solutions combining these can be mentioned.
  • the content of the pH adjuster in the latent heat storage material integrated activated carbon is the total amount of the latent heat storage material integrated activated carbon from the viewpoint of easily improving the uniformity of the binder on the surface of the activated carbon and easily improving the hardness.
  • 100% by mass 0 to 10% by mass is preferable, and 0 to 5% by mass is more preferable.
  • the activated carbon-containing layer containing activated carbon may be composed of only the above-mentioned activated carbon and, if necessary, organic binder B, or a cross-linking agent, a coloring agent, a plasticizing agent, a stabilizer, and a mold release agent (stearic acid).
  • Additives such as (metal soap such as zinc acid acid) may be contained.
  • the content of such an additive is preferably in a range that does not impair the effects of the present invention, and is preferably 0 to 10% by mass, more preferably 0 to 5% by mass, with the total amount of the activated carbon-containing layer being 100% by mass. It is preferable, and 0 to 3% by mass is more preferable.
  • the pH of the activated carbon-containing layer is, for example, in the state of a carboxylate under neutral and basic conditions and is easily dissolved in water, so that it is easy to improve the uniformity of the binder on the surface of the activated carbon and improve the hardness.
  • the pH of the aqueous suspension of the activated carbon-containing layer measured in accordance with JIS K 1474 (2014) is preferably 4.5 or higher, more preferably 5.5 or higher. It is preferable, and 6.0 or more is more preferable.
  • the upper limit of the pH of the aqueous suspension of the activated carbon-containing layer measured in accordance with JIS K 1474 (2014) is not particularly limited, but is usually about 14.0.
  • the thickness of the activated carbon-containing layer containing activated carbon is not particularly limited, but it is easy to suppress the temperature rise due to the heat of adsorption of the activated carbon, it is easy to improve the latent heat amount, and it is easy to improve the adsorption performance and durability. From the viewpoint of easy improvement, 180 to 2050 ⁇ m is preferable, 250 to 900 ⁇ m is more preferable, and 350 to 780 ⁇ m is further preferable.
  • the thickness of the activated carbon-containing layer is measured with a caliper after breaking the monolithic coal and removing the heat storage material.
  • the shape of the latent heat storage material-integrated activated carbon of the present invention described above is not particularly limited, but for example, according to the manufacturing method described later, it tends to be spherical or elliptical spherical.
  • the average particle size of the activated carbon integrated with the latent heat storage material of the present invention is not particularly limited, but it is easy to suppress the temperature rise due to the adsorption heat of the activated carbon, it is easy to improve the latent heat amount, it is easy to improve the adsorption performance, and it is durable. From the viewpoint of easily improving the property, easily lowering the ventilation resistance, and easily improving the air flow in the canister, 1.0 to 4.0 mm is preferable, 1.2 to 3.4 mm is more preferable, and 1. 7 to 2.8 mm is more preferable.
  • the average particle size of the latent heat storage material-integrated activated carbon of the present invention is sieved using a low tap and a sieve according to JIS K1474 (2014), and the mass average particle size is calculated.
  • the calorific value of the latent heat storage material-integrated activated carbon of the present invention can be 10 to 100 J / g, preferably 11 to 80 J / g, and more preferably 12 to 60 J / g. Therefore, the activated carbon integrated with the latent heat storage material of the present invention can easily suppress the temperature rise due to the heat of adsorption of the activated carbon, and can easily improve the adsorption / desorption performance, durability, hardness, and the like.
  • the calorific value of the latent heat storage material is measured by DSC7020 (differential scanning calorimeter, manufactured by Seiko Instruments Inc.).
  • the pH of the activated carbon integrated with the latent heat storage material of the present invention is, for example, in the state of a carboxylic acid salt under neutral and basic conditions and is easily dissolved in water. Easy to improve. Therefore, although not particularly limited, the pH of the aqueous suspension of the latent heat storage material-integrated activated carbon of the present invention measured in accordance with JIS K 1474 (2014) is preferably 4.5 or more. 5.5 or more is more preferable, and 6.0 or more is further preferable.
  • the upper limit of the pH of the aqueous suspension of the latent heat storage material-integrated activated carbon of the present invention measured in accordance with JIS K 1474 (2014) is not particularly limited, but is usually about 14.0.
  • the latent heat storage material integrated activated carbon of the present invention thus obtained can have a high hardness.
  • the ASTM hardness of the latent heat storage material-integrated activated carbon of the present invention is preferably 45% or more, more preferably 48 to 80%, and even more preferably 50 to 80%.
  • the ASTM hardness of the latent heat storage material integrated activated carbon of the present invention is measured according to ASTM-D5228.
  • the latent heat storage material-integrated activated carbon of the present invention thus obtained can increase the butane activity (BA) indicating the fuel evaporation gas adsorption performance.
  • the butane activity (BA) of the latent heat storage material-integrated activated carbon of the present invention is preferably 42% or more, more preferably 43 to 60%, still more preferably 44 to 53%. It is known that when butane activity (BA) is 42% or more, the fuel evaporation gas adsorption performance is excellent.
  • the butane activity (BA) of the latent heat storage material-integrated activated carbon of the present invention is measured according to ASTM-D5228.
  • the latent heat storage material-integrated activated charcoal of the present invention as described above can be filled in a canister container, and the vaporized fuel gas from the fuel tank is introduced into the container to form a canister and adsorb the vaporized fuel gas.
  • the canister that adsorbs the evaporated fuel generated in the fuel tank is not particularly limited, and an existing one can be used.
  • automobile applications include closed fuel tanks and canisters connected to ordinary fuel tanks. The connection between the closed fuel tank or the normal fuel tank and the canister can be directly connected or indirectly connected via a blocking valve or an opening valve between them.
  • the temperature of the gas and the container is preferably equal to or lower than the phase change temperature (usually the melting point) of the phase change substance. That is, the latent heat storage material integrated activated carbon of the present invention is useful as a latent heat storage material integrated activated carbon for canisters.
  • Examples of the vaporized fuel gas to which the latent heat storage material-integrated spherical activated carbon of the present invention can be applied include hydrocarbon-based, ketone, halogen-based, alcohol, ester, and gasoline for automobiles, which are often used in solvent recovery.
  • the method for producing activated carbon integrated with latent heat storage material of the present invention is not particularly limited, but for example.
  • the microcapsule composition obtained in step (1) is coated with the thermosetting organic binder A and heat-treated to obtain the above.
  • the process of obtaining latent heat storage material, (3) It can be produced by a method including a step of mixing and granulating the latent heat storage material obtained in the step (2) and the composition containing the activated carbon.
  • Step (1) In the step (1), first, the microcapsules and the thermosetting organic binder A are mixed. Specifically, in step (1), it is preferable that the microcapsules and the thermosetting organic binder A are mixed, then extruded and granulated, and then granulated. The thermosetting organic binder A at this time is not coated on the surface of the microcapsules, but is used for mixing with the microcapsules.
  • the amount of the heat-curable organic binder A added makes it easy to improve the binding force of the latent heat storage material obtained in the step (2), easily improves the hardness and solvent resistance, and makes it difficult for the microcapsules to be broken.
  • 5 to 30 parts by mass is preferable with respect to 100 parts by mass of the microcapsules. 8 to 25 parts by mass is more preferable, and 10 to 20 parts by mass is further preferable.
  • the method of mixing the microcapsules and the thermosetting organic binder A is not particularly limited.
  • microcapsules and a thermosetting organic binder A may be mixed in a solvent in a conventional manner to form a slurry.
  • the solvent that can be used at this time is not particularly limited, and general solvents can be used, and examples thereof include water, alcohol (methanol, ethanol, etc.), and a mixed solution thereof.
  • a solvent may not be used.
  • the amount of the solvent added is preferably 3 to 50 parts by mass with respect to 100 parts by mass of the microcapsules from the viewpoint of easily suppressing cracks and powdering after molding and increasing the packing density of the microcapsules. By mass is more preferred, and 10 to 20 parts by mass is even more preferred.
  • the total amount including the solvent present in the thermosetting organic binder A can be within the above range. ..
  • the extrusion granulation is not particularly limited and can be performed by a conventional method, and a general granulation machine such as a stirring granulation machine, a compression granulation machine, an extrusion granulation machine, or a rolling granulation machine is used.
  • a general granulation machine such as a stirring granulation machine, a compression granulation machine, an extrusion granulation machine, or a rolling granulation machine is used.
  • a die such as a screen die, a disk die, or a dome-shaped die is used to granulate the latent heat storage material to a desired size, and further, a pan-type granulator or a drum mixer. , It can be sized by rolling at about 50 to 1000 rpm using a mulmerizer or the like.
  • Step (2) is a step of coating the microcapsule composition obtained in the step (1) with a thermosetting organic binder A and heat-treating the microcapsule composition to obtain a latent heat storage material.
  • thermosetting organic binder A used at this time may be the same as the thermosetting organic binder A used in the step (1), or may be different.
  • the latent heat storage material after the thermosetting organic binder A is cured uses the thermosetting organic binder A having high solvent resistance (water resistance, organic solvent resistance, etc.).
  • solvent resistance water resistance, organic solvent resistance, etc.
  • the cured latent heat storage material does not become turbid even when immersed in water at 50 ° C. for 24 hours, and further, it does not become turbid even when immersed in water at 70 ° C. for 24 hours. More preferred.
  • the organic solvent resistance after the cured latent heat storage material is immersed in an organic solvent at 30 ° C.
  • the amount of the phase change substance exuded into the organic solvent is the latent heat. It is preferably 15% by mass or less, and more preferably 10% by mass or less, based on the total amount of the phase changing substance in the heat storage material.
  • a thermosetting resin binder having water resistance such as a phenol resin, an acrylic resin, a melamine resin, and an amide ester resin is preferable.
  • the amount of the heat-curable organic binder A added to coat the microcapsule composition obtained in the step (1) is likely to suppress a temperature rise due to the heat of adsorption of the activated charcoal, easily improve the amount of latent heat, and easily improve the adsorption performance.
  • the total amount of the microcapsule composition obtained in the step (1) is 100 parts by mass, preferably 0.5 to 10 parts by mass, and more preferably 1 to 5 parts by mass. .5 to 3 parts by mass is more preferable.
  • the method of coating the microcapsule composition obtained in the step (1) with the thermosetting organic binder A is not particularly limited.
  • it can be coated in a solvent using a one-fluid nozzle, a two-fluid nozzle, or the like.
  • the solvent that can be used at this time is not particularly limited, and general solvents can be used, and examples thereof include water, alcohol (methanol, ethanol, etc.), and a mixed solution thereof.
  • a solvent may not be used.
  • the amount of the solvent added is from the viewpoint that it is easy to suppress cracking and pulverization after molding, it is easy to suppress the temperature rise due to the adsorption heat of activated carbon, it is easy to improve the latent heat amount, it is easy to improve the adsorption performance, and it is easy to improve the durability. Therefore, the total amount of the microcapsule composition obtained in the step (1) is 100 parts by mass, preferably 0.5 to 10 parts by mass, more preferably 1 to 5 parts by mass, and further 1.5 to 3 parts by mass. preferable.
  • the thermosetting organic binder A is in the form of a solution, a dispersion, a suspension, or the like, the total amount including the solvent present in the thermosetting organic binder A can be within the above range. ..
  • the heating temperature during the heat treatment is not particularly limited, and is 100 to 300 ° C. from the viewpoint that it is easy to suppress the temperature rise due to the adsorption heat of the activated carbon, it is easy to improve the latent heat amount, it is easy to improve the adsorption performance, and it is easy to improve the durability. Is preferable, and 150 to 250 ° C. is more preferable.
  • the heating time during the heat treatment is not particularly limited, and it is easy to complete the curing reaction and improve the durability. Therefore, 30 to 180 minutes is preferable, and 60 to 150 minutes is more preferable.
  • thermosetting organic binder A can be cured to obtain a latent heat storage material.
  • Step (3) is a step of mixing and granulating the latent heat storage material obtained in the step (2) and the composition containing activated carbon. Thereby, the latent heat storage material obtained in the step (2) can be coated with the activated carbon-containing layer to produce the latent heat storage material integrated activated carbon of the present invention.
  • the composition containing activated carbon can form the above-mentioned activated carbon-containing layer, and can contain the above-mentioned organic binder B and pH adjuster, if necessary, in addition to the activated carbon.
  • the content of the organic binder B is such that the temperature rise due to the heat of adsorption of the activated carbon can be easily suppressed, the amount of latent heat can be easily improved, the adsorption performance can be easily improved, and the durability can be easily improved.
  • 100 parts by mass 0.5 to 20 parts by mass is preferable, and 6 to 11 parts by mass is more preferable.
  • the content of the pH adjuster is preferably 0 to 10 parts by mass with respect to 100 parts by mass of activated carbon from the viewpoint of easily improving the uniformity of the binder on the surface of the activated carbon and easily improving the hardness. , 0-5 parts by mass is more preferable.
  • the washing method may be a general washing method of chemical-activated charcoal.
  • phosphoric acid-activated charcoal it can be washed with hot water or cold water and dried.
  • a basic aqueous solution such as an ammonium carbonate aqueous solution may be used instead of hot water or cold water.
  • the composition containing activated carbon may contain a solvent from the viewpoint of easily suppressing cracking and pulverization after molding.
  • the solvent that can be used at this time is not particularly limited, and general solvents can be used, and examples thereof include water, alcohol (methanol, ethanol, etc.), and a mixed solution thereof.
  • a solvent may not be used.
  • the amount of the solvent added is easy to suppress cracking and pulverization after molding, easy to suppress the temperature rise due to the adsorption heat of activated carbon, easy to improve the latent heat amount, easy to improve the adsorption performance, and easy to improve the durability. Therefore, 50 to 1500 parts by mass is preferable, 100 to 500 parts by mass is more preferable, and 300 to 650 parts by mass is further preferable with respect to 100 parts by mass of activated carbon.
  • the organic binder B is in the form of a solution, a dispersion, a suspension, or the like, the total amount including the solvent present in the organic binder B can be in the above range.
  • the latent heat storage material obtained in the step (2) and the composition containing activated carbon are mixed and granulated (the latent heat storage material obtained in the step (2) is coated with the activated carbon-containing layer).
  • the extrusion granulation method is a method in which a binder is added to a composition containing a latent heat storage material and activated charcoal obtained in step (2) and kneaded, and the kneaded product is extruded from a screen to form and granulate.
  • the crushing and granulating method which is a method in which the kneaded mass prepared by kneading in the above method is cut with a rotary blade of a granulator and ejected from the outer screw eyes by centrifugal force; obtained in step (2).
  • Rolling granulation method which is a method of obtaining particles close to spheres by applying a rotating motion or vibration to a humidified powder by adding a binder to a composition containing a latent heat storage material and activated charcoal to agglomerate the powder.
  • the fluidized layer granulation method is a method in which the obtained composition containing the latent heat storage material and the activated charcoal is flowed from below by a hot air stream, and a binder is sprayed onto the composition to granulate the composition; the latent heat obtained in the step (2).
  • An unlimited example of a stirring granulation method in which a composition containing a heat storage material and activated charcoal is put into a container and water or a granulating liquid is added while stirring with a rotating blade to agglomerate raw material powders and granules into a spherical shape. be able to. At this time, it can be molded by using a mulmerizer, spray granulation, fluidized bed granulation, stirring granulation machine, bread type granulation machine and the like.
  • the amount of the composition containing activated carbon to be used is not particularly limited, and it is easy to suppress cracking and pulverization after molding, it is easy to suppress the temperature rise due to the heat of adsorption of activated carbon, and it is easy to improve the amount of latent heat to improve the adsorption performance. From the viewpoint of easy improvement and easy improvement of durability, 200 to 1000 parts by mass is preferable, and 250 to 600 parts by mass is more preferable with respect to 100 parts by mass of the latent heat storage material obtained in the step (2).
  • the binder is not particularly limited, and for example, cellulose derivatives such as methyl cellulose, ethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, hypromellose, and carboxymethyl cellulose; crystalline cellulose, polyvinyl alcohol, polyvinylpyrrolidone (povidone), and vinylpyrrolidone are used. Examples thereof include polymers (copolyvidone), acrylic acid-based polymers, gelatin, gum arabic, purulan, canten, tragant, sodium alginate, propylene glycol alginate, pregelatinized starch, dextrin, macrogol, and sucrose. These binders can also be used in the form of a solution such as an aqueous solution. These binders can be used alone or in combination of two or more.
  • the amount of the above binder used is 15 to 100 parts by mass in terms of solid content with respect to 100 parts by mass of the latent heat storage material obtained in step (2) from the viewpoint of easily suppressing cracks and powdering after molding. Preferably, 17 to 85 parts by mass is more preferable.
  • the heating temperature during the heat treatment is not particularly limited, and is 80 to 250 ° C. from the viewpoint that it is easy to suppress the temperature rise due to the adsorption heat of the activated carbon, it is easy to improve the latent heat amount, it is easy to improve the adsorption performance, and it is easy to improve the durability. Is preferable, and 100 to 200 ° C. is more preferable.
  • the heating time during the heat treatment is not particularly limited, and can be set to a time during which a spherical activated carbon having a sufficiently small particle size and high sphericity can be obtained. From the viewpoint of easy improvement, easy improvement of adsorption performance and easy improvement of durability, 10 minutes to 12 hours is preferable, and 30 minutes to 6 hours is more preferable. At this time, it is preferable to adjust the water content of the obtained latent heat storage material-integrated activated carbon of the present invention to be 10% by mass or less, particularly 5% by mass or less.
  • the average particle size of the microcapsules was measured by a laser diffraction type particle size distribution measuring device (Microtrack Bell Co., Ltd .: Microtrack MT3300EXII), and the average cross section of the latent heat storage material was measured.
  • the diameter was measured for 10 pellets with a caliper, and the calorific value of the latent heat storage material was measured with a DSC7020 (differential scanning calorimeter, manufactured by Seiko Instruments Co., Ltd.).
  • the "existing method” is an in-situ method using an initial condensate of a formalin condensation type resin. It means that the microcapsules were prepared by the above operation: The sodium salt aqueous solution of the styrene anhydride maleic acid copolymer whose pH was adjusted to 4.5 was vigorously stirred with a homomixer, and the phase change substance was twice that of the above emulsion. A predetermined phase transition substance having a predetermined phase transition temperature was gradually added so as to have the number of moles of the above, and emulsification was performed until the average particle size became 3.0 to 4.0 ⁇ m.
  • melamine formaldehyde: water was mixed so as to have a molar number of 1: 2: 7, adjusted to pH 10, and heated to 60 ° C. with stirring to obtain an initial condensate.
  • the above emulsion is transferred to a separate container, the melamine formalin initial condensate is added, and the mixture is reacted at 80 ° C. for 3 hours to obtain a microcapsule aqueous dispersion in which the ratio of the melamine film to the microcapsules is 17%. Solid content (40% by weight) was obtained, the pH was adjusted to 9, and encapsulation was performed.
  • Polyvinyl alcohol was added so as to be 0.5% by mass with respect to the aqueous dispersion of the microcapsules, the mixture was stirred again, and then dried by a spray-drying method to obtain microcapsules.
  • the activated carbon weighs 1.0 g
  • the latent heat storage material integrated activated carbon and the molded products of the production example and the comparative production example are 3 0.0 g was added to 100 mL of water, heated for 5 minutes so that boiling continued, cooled to room temperature, and the pH of the aqueous suspension obtained by adding water to 100 mL was measured using a pH meter.
  • Example 1 Microcapsules covered with a melamine membrane prepared by an existing method containing a linear aliphatic hydrocarbon having a phase transition temperature of 50 to 52 ° C. were used.
  • thermosetting phenol-based organic binder phenolite 1480 manufactured by DIC Corporation; solid content 68.7% by mass
  • 18 parts by mass of water were added. And mixed. Then, the mixture was molded by an extruder (disc pelleter F5 type manufactured by Dalton Co., Ltd.). At this time, the opening of the screen die was finely divided using 1.0 mm. Then, using Malmerizer (QJ-400 type manufactured by Dalton Co., Ltd.), the granules were sized for 2 minutes at 275 rpm to obtain a microcapsule composition.
  • the obtained microcapsule composition was used and coated with a thermosetting phenolic binder similar to the above. Specifically, 1.5 parts by mass of the heat-curable phenolic binder and an equal amount of water as a solvent were added to 100 parts by mass of the obtained microcapsule composition, and a one-fluid nozzle was used. The microcapsules were coated with a heat-curable phenolic solvent, the material temperature was set to 160 ° C. or higher, and the cells were dried for 2 hours to obtain a latent heat storage material.
  • the activated carbon, the organic binder and water were kneaded in advance and crushed to obtain a mixture (composition containing activated carbon).
  • the organic binder carboxymethyl cellulose sodium salt (F30MC manufactured by Nippon Paper Co., Ltd.), Epocross WS-700 (oxazoline group-containing water-soluble polymer manufactured by Nippon Catalyst Co., Ltd.), ADEKA Resin (ADEKA Corporation) Made of water-based epoxy resin EM-0180) was selected, and the solid content was 7.2 parts by mass, 1.2 parts by mass, and 2.1 parts by mass, for a total of 10.5 parts by mass with respect to 100 parts by mass of activated carbon. 160.5 parts by mass of water was added to 100 parts by mass of activated charcoal.
  • Example 2 A latent heat storage material as in Example 1, except that microcapsules covered with a melamine film prepared by an existing method using a linear aliphatic hydrocarbon having a phase transition temperature of 45 to 47 ° C. were used. Got Then, in the same manner as in Example 1, the latent heat storage material integrated activated carbon of Example 2 was obtained.
  • Example 3 Using microcapsules covered with a melamine film prepared by an existing method using a linear aliphatic hydrocarbon (22 carbon atoms) having a phase transition temperature of 42 to 45 ° C., the opening of the screen die is 0.
  • Example 4 Same as in Example 1 except that microcapsules covered with a melamine film prepared by an existing method using a linear aliphatic hydrocarbon (carbon number 22) having a phase transition temperature of 42 to 45 ° C. were used as inclusions. In addition, a latent heat storage material was obtained. Then, in the same manner as in Example 1, the latent heat storage material integrated activated carbon of Example 4 was obtained.
  • a linear aliphatic hydrocarbon carbon number 22 having a phase transition temperature of 42 to 45 ° C.
  • Example 5 Using microcapsules covered with a melamine film prepared by an existing method using a linear aliphatic hydrocarbon (22 carbon atoms) having a phase transition temperature of 42 to 45 ° C., the opening of the screen die is 1.
  • Example 6 Same as in Example 1 except that microcapsules covered with a melamine film prepared by an existing method using a linear aliphatic hydrocarbon (carbon number 20) having a phase transition temperature of 32 to 37 ° C. were used as inclusions. In addition, a latent heat storage material was obtained. Then, in the same manner as in Example 1, the latent heat storage material integrated activated carbon of Example 6 was obtained.
  • Example 7 Similar to Example 1, except that microcapsules covered with a melamine film prepared by an existing method using a linear aliphatic hydrocarbon (16 carbon atoms) having a phase transition temperature of 18 ° C. as an inclusion were used. A latent heat storage material was obtained. Then, in the same manner as in Example 1, the latent heat storage material integrated activated carbon of Example 7 was obtained.
  • Comparative Example 1 The microcapsules used in Example 1 were used as microcapsules covered with a melamine membrane prepared by an existing method using a linear aliphatic hydrocarbon having a phase transition temperature of 50 to 52 ° C. as an inclusion. A microcapsule composition was produced in the same manner as in Example 1 and used as a latent heat storage material. That is, the surface of the microcapsules was not coated with a thermosetting organic binder. Then, in the same manner as in Example 1, the latent heat storage material integrated activated carbon of Comparative Example 1 was obtained.
  • Comparative Example 2 A microcapsule composition was prepared in the same manner as in Example 1 using microcapsules covered with a melamine film prepared by an existing method using a linear aliphatic hydrocarbon having a phase transition temperature of 45 to 47 ° C. as an inclusion. Manufactured and used as a latent heat storage material. That is, the surface of the microcapsules was not coated with a thermosetting organic binder. Then, in the same manner as in Example 1, the latent heat storage material integrated activated carbon of Comparative Example 2 was obtained.
  • Comparative Example 3 Similar to Example 1, using microcapsules covered with a melamine film prepared by an existing method using a linear aliphatic hydrocarbon (carbon number 22) having a phase transition temperature of 42 to 45 ° C. as an inclusion. A microcapsule composition was produced and used as a latent heat storage material. That is, the surface of the microcapsules was not coated with a thermosetting organic binder. Then, in the same manner as in Example 1, the latent heat storage material integrated activated carbon of Comparative Example 3 was obtained.
  • a linear aliphatic hydrocarbon carbon number 22
  • Comparative Example 4 Similar to Example 1, using microcapsules covered with a melamine film prepared by an existing method using a linear aliphatic hydrocarbon (carbon number 20) having a phase transition temperature of 32 to 37 ° C. as an inclusion. A microcapsule composition was produced and used as a latent heat storage material. That is, the surface of the microcapsules was not coated with a thermosetting organic binder. Then, in the same manner as in Example 1, the latent heat storage material integrated activated carbon of Comparative Example 4 was obtained.
  • a linear aliphatic hydrocarbon carbon number 20
  • Comparative Example 5 Using a microcapsule covered with a melamine film prepared by an existing method using a linear aliphatic hydrocarbon (16 carbon atoms) having a phase transition temperature of 18 ° C., the microcapsule is the same as in Example 1. The composition was produced and used as a latent heat storage material. That is, the surface of the microcapsules was not coated with a thermosetting organic binder. Then, in the same manner as in Example 1, the latent heat storage material integrated activated carbon of Comparative Example 5 was obtained.
  • Comparative Example 6 Using microcapsules covered with a melamine film prepared by an existing method using a linear aliphatic hydrocarbon (22 carbon atoms) having a phase transition temperature of 42 to 45 ° C., the opening of the screen die is opened.
  • a latent heat storage material was obtained in the same manner as in Example 1 except that the particles were finely divided using 0.7 mm.
  • the activated carbon integrated with the latent heat storage material was obtained.
  • Test Example 1 3 g of the latent heat storage material integrated activated carbon obtained in Examples 1 to 7 and Comparative Examples 1 to 6 was charged into a portable reactor pressure-resistant container (TVS-1 type manufactured by Pressure-Resistant Glass Industry Co., Ltd.), and 10 mL of gasoline was charged. .. Then, after heat-treating at 70 ° C. for 48 hours, the activated carbon integrated with the latent heat storage material was taken out on a petri dish, washed with 30 mL of hexane (special grade reagent manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), and then blown. It was dried at 40 ° C. for 2 hours using a low temperature dryer (DK340S manufactured by Yamato Scientific Co., Ltd.).
  • a portable reactor pressure-resistant container (TVS-1 type manufactured by Pressure-Resistant Glass Industry Co., Ltd.)
  • 10 mL of gasoline was charged. ..
  • the activated carbon integrated with the latent heat storage material was taken out on a pe
  • the calorific value was measured using DSC7020 (differential scanning calorimeter, manufactured by Seiko Instruments Inc.). The calorific value after gasoline treatment was divided by the calorific value at the time of untreatment to calculate the calorific value residual ratio. The results are shown in Table 1.
  • thermosetting organic binder By comparing Examples 1 to 7 and Comparative Examples 1 to 5, the outer surface of the microcapsules is coated with a thermosetting organic binder, so that the residual rate of the amount of heat possessed by the latent heat storage material after the gasoline immersion test Is as high as 93% or more, and it can be seen that the residual amount of heat is significantly reduced without coating (53 to 56%). From this, it can be seen that the effect of coating the microcapsules with a thermosetting organic binder is high. Furthermore, the same tendency was obtained regardless of the type of phase change substance.
  • the latent heat storage material in the latent heat storage material integrated activated carbon coated with the thermosetting organic binder (Example 4) and the latent heat storage material integrated activated carbon not coated with the heat curable organic binder (Comparative Example 3).
  • 1 and 2 show a comparison of SEM images of the latent heat storage material in).
  • the one in which the activated carbon-containing layer on the surface was peeled off from each latent heat storage material integrated activated carbon by hitting with a hammer was evaluated. It can be seen that those coated with a thermosetting organic binder have less cracks, and those not coated with a thermosetting organic binder have more cracks, and the inclusions inside are removed by the solvent, reducing the amount of residual heat. ..
  • Example 8 A mixture (composition containing activated carbon) was obtained by kneading activated carbon, an organic binder, and water in advance and crushing the mixture.
  • the organic binder carboxymethyl cellulose sodium salt (F30MC manufactured by Nippon Paper Co., Ltd.), Epocross WS-700 (oxazoline group-containing water-soluble polymer manufactured by Nippon Catalyst Co., Ltd.), ADEKA Resin Co., Ltd.
  • ADEKA Made of water-based epoxy resin EM-0180 was selected, and the solid content was 7.2 parts by mass, 1.2 parts by mass, and 2.1 parts by mass, for a total of 10.5 parts by mass with respect to 100 parts by mass of activated carbon. 160.5 parts by mass of water was added to 100 parts by mass of activated charcoal.
  • BA butane activity representing fuel evaporation gas adsorption performance: Measured in accordance with ASTM-D5228 (hereinafter abbreviated as BA).
  • the spherical activated carbon integrated with the latent heat storage material to be provided was limited to those having an average particle size of 2.36 mm or more and less than 2.80 mm. The results are shown in Tables 2 and 3.
  • Example 11 The latent heat storage material obtained in Example 4 was used as the core as the latent heat storage material, and the activated charcoal mixture (composition containing active charcoal) was applied to a coating (thickness 1000 ⁇ m) so that the entire amount of 2854 g was used (latent heat storage material).
  • Material: Activated charcoal: Organic binder 250: 2583: 270 (mass ratio))
  • the latent heat storage material integrated activated charcoal of Example 11 was obtained in the same manner as in Example 8.
  • sieving is performed using a sieve having a size of 3.5 (opening 5.6 mm) to 10Mesh (opening 1.7 mm) (JIS standard), and is arbitrary except for a section larger than the target particle size and a section finer than 10Mesh. Spherical activated carbon integrated with latent heat storage material was obtained.
  • Example 12 The latent heat storage material obtained in Example 4 was used as the core as the latent heat storage material, and an activated charcoal mixture (composition containing active charcoal) was applied to a coating (thickness 840 ⁇ m) so that the entire amount of 2000 g was used (latent heat storage material).
  • Material: Activated charcoal: Organic binder 250: 1811: 189 (mass ratio))
  • the latent heat storage material integrated activated charcoal of Example 12 was obtained in the same manner as in Example 11.
  • Example 13 The latent heat storage material obtained in Example 4 was used as the core as the latent heat storage material, and the activated charcoal mixture (composition containing active charcoal) was applied to a coating (thickness 680 ⁇ m) so that the entire amount of 1347 g was used (latent heat storage material).
  • Material: Activated charcoal: Organic binder 250: 1220: 127 (mass ratio))
  • a latent heat storage material-integrated activated charcoal of Example 12 was obtained.
  • Example 14 The latent heat storage material obtained in Example 5 was used as the core as the latent heat storage material, and an activated charcoal mixture (composition containing active charcoal) was applied to a coating (thickness 560 ⁇ m) so that 691 g of the mixture was used in its entirety (latent heat storage material).
  • Material: Activated charcoal: Organic binder 250: 625: 65 (mass ratio))
  • the latent heat storage material integrated activated charcoal of Example 12 was obtained in the same manner as in Example 11.
  • Reference example 1 An existing activated carbon (BAX1100 manufactured by Industry Corporation) that does not use a latent heat storage material was used.
  • Reference example 2 An existing activated carbon (BAX1700 manufactured by Industry Corporation) that does not use a latent heat storage material was used.
  • Test Example 4 The ASTM hardness was measured with reference to ASTM-D5228. The results are shown in Table 3.
  • the activated carbon As the activated carbon, activated carbon having a pH of 4.19 in an aqueous suspension measured according to JIS K 1474 (2014) was used. This activated carbon, an organic binder, and water are mixed and molded with a die having a hole diameter of 2.2 mm and a thickness of 15 mm using an extruder (disc pelleter F5 type manufactured by Dalton Co., Ltd.), and a malmerizer (Dalton, By finely granulating with Q-400T), a molded product having the same material composition as the activated carbon-containing layer of the heat storage material-integrated activated carbon was obtained. The pH of the obtained molded product was 4.97, which was the pH of the aqueous suspension measured according to JIS K 1474 (2014).
  • the organic binder examples include carboxymethyl cellulose sodium salt (F30MC manufactured by Nippon Paper Co., Ltd.), Epocross WS-700 (oxazoline group-containing water-soluble polymer manufactured by Nippon Catalyst Co., Ltd.), and ADEKA Resin (manufactured by ADEKA Corporation).
  • Aqueous epoxy resin EM-0180 was selected, and the solid content was 6.8 parts by mass, 1.2 parts by mass, and 1.9 parts by mass, for a total of 9.9 parts by mass and water, respectively, with respect to 100 parts by mass of activated carbon. Added 220.0 parts by mass with respect to 100 parts by mass of activated charcoal.
  • Manufacturing example 2 Measured in accordance with JIS K 1474 (2014) Measured in accordance with JIS K 1474 (2014) in the same manner as in Production Example 1 except that activated carbon having a pH of 4.50 in the aqueous suspension is used. A molded product having a pH of 5.87 was obtained.
  • the pH of the obtained molded product was 10.43, which was the pH of the aqueous suspension measured according to JIS K 1474 (2014).
  • the organic binder include carboxymethyl cellulose sodium salt (F30MC manufactured by Nippon Paper Co., Ltd.), Epocross WS-700 (oxazoline group-containing water-soluble polymer manufactured by Nippon Catalyst Co., Ltd.), and ADEKA Resin (manufactured by ADEKA Corporation).
  • Aqueous epoxy resin EM-0180 was selected, and the solid content was 6.8 parts by mass, 1.2 parts by mass, and 1.9 parts by mass, for a total of 9.9 parts by mass and water with respect to 100 parts by mass of activated carbon. Added 215.0 parts by mass with respect to 100 parts by mass of activated charcoal.
  • Comparative manufacturing example 1 Measured in accordance with JIS K 1474 (2014) Measured in accordance with JIS K 1474 (2014) in the same manner as in Production Example 1 except that activated charcoal having a pH of 2.92 in the aqueous suspension is used. A molded product having a pH of 2.88 was obtained.
  • Test Example 5 The ASTM hardness was measured with reference to ASTM-D5228. The results are shown in Table 4. In Table 4, the case where the pH of each molded product was 4.5 or more was designated as A, and the case where the pH was less than 4.5 was designated as B.

Abstract

This latent heat storage material-integrated active carbon contains an active carbon and a latent heat storage material having a microcapsule in which a phase-transition material, which absorbs and releases latent heat according to temperature, is encapsulated, wherein: in the latent heat storage material, the surface of the microcapsule is coated with an organic binder-containing layer including a thermosetting organic binder A; and the surface of the latent heat storage material is coated with an active carbon-containing layer. The latent heat storage material-integrated active carbon is an adsorbent which can prevent a heat transfer loss in voids between particles by integrating the latent heat storage material and the active carbon while suppressing damage to the latent heat storage material compared to the case of simply mixing a latent heat storage material and active carbon pellets, and which can maintain a high level of adsorption/desorption performance and durability by effectively controlling adsorption heat.

Description

潜熱蓄熱材一体型活性炭及びその製造方法Latent heat storage material integrated activated carbon and its manufacturing method
　本発明は、潜熱蓄熱材一体型活性炭及びその製造方法に関する。 The present invention relates to an activated carbon integrated with a latent heat storage material and a method for producing the same.
　有害大気汚染物質に対する排出濃度規制の強化に伴い、有機溶剤含有ガス処理装置の需要が高まっている。なかでも有機溶剤を液化回収する有機溶剤回収システムは、有機溶剤を燃焼して無害化する燃焼装置よりも二酸化炭素排出量が少なく、また回収した有機溶剤を再利用できる等の利点がある。 Demand for organic solvent-containing gas treatment equipment is increasing with the tightening of emission concentration regulations for harmful air pollutants. Among them, the organic solvent recovery system that liquefies and recovers the organic solvent has advantages that the amount of carbon dioxide emitted is smaller than that of the combustion device that burns and detoxifies the organic solvent, and that the recovered organic solvent can be reused.
　有機溶剤回収システムは、吸着材で被処理ガス中の有機溶剤を吸着除去する吸着工程と、加熱空気等の不活性ガスによって吸着材に吸着された有機溶剤を脱着する脱着工程とを実行し、この吸着工程と脱着工程を時間的に交互に行う切替え手段または連続的に行う手段を設けて構成されている。 The organic solvent recovery system executes an adsorption step of adsorbing and removing the organic solvent in the gas to be treated with the adsorbent and a desorption step of desorbing the organic solvent adsorbed on the adsorbent by an inert gas such as heated air. It is configured by providing a switching means or a means for continuously performing the adsorption step and the desorption step alternately in time.
　燃料蒸発ガスに対する規制は、各国、各地域で行われており、この燃料蒸発ガス規制は，近年見られる大気汚染問題の深刻化に伴いその規制が強化されている傾向にある。大気汚染物質発生源の一つである自動車が大気に放出する排出ガスには、燃料をエンジンで燃焼させた排気ガス、走行時にタイヤが巻き上げる巻き上げ粉塵、自動車に搭載した燃料、自動車の材料の溶剤等から発生する蒸発ガス等がある。 Regulations on fuel evaporative gas are enforced in each country and region, and this fuel evaporative gas regulation tends to be strengthened as the air pollution problem seen in recent years becomes more serious. Exhaust gas emitted to the atmosphere by automobiles, which is one of the sources of air pollutants, includes exhaust gas from fuel burned by an engine, hoisting dust that tires wind up while driving, fuel mounted on automobiles, and solvents for automobile materials. There is exhaust gas etc. generated from such as.
　自動車部品であるキャニスターは、燃料タンク内で蒸発したガソリンベーパを一時的に活性炭に吸着（捕集）し、車外への排出を抑制する。一時的に活性炭に吸着（捕集）したベーパは、走行時にエンジンの吸気管負圧を利用してパージ（掃気）し、エンジンで燃焼処理することで繰り返し性能が維持できるように構成されている。 The canister, which is an automobile part, temporarily adsorbs (collects) the gasoline vapor evaporated in the fuel tank to the activated carbon and suppresses the discharge to the outside of the vehicle. The vapor temporarily adsorbed (collected) on the activated carbon is purged (scavenged) by using the negative pressure of the intake pipe of the engine during running, and is configured so that the performance can be maintained repeatedly by burning the engine. ..
　このように吸着材に高品質の吸脱着性能が求められる用途は様々あるが、吸着材自体が低温ほど吸着能が高くなり、高温ほど脱着能が高くなるという性質があるため、高品質品が求められる際に重要な問題となる因子の一つが温度である。 In this way, there are various applications in which the adsorbent is required to have high-quality adsorption / desorption performance, but the adsorbent itself has the property that the lower the temperature, the higher the adsorption capacity, and the higher the temperature, the higher the desorption ability. One of the important factors when sought is temperature.
　従来から、各種のガス、液体、蒸気等が吸着材に吸脱着の際に出入りする熱は、外部より水等の媒体を流すことにより温度を制御するか、熱伝導率の高い物質を挿入する等して熱容量の高い物質を混合し温度上昇を抑えることは可能であるが設備が重量化、大型化する。 Conventionally, the heat that goes in and out of the adsorbent when various gases, liquids, vapors, etc. are attached to and detached from the adsorbent is controlled by flowing a medium such as water from the outside, or a substance with high thermal conductivity is inserted. Although it is possible to suppress the temperature rise by mixing substances with high heat capacity, the equipment becomes heavier and larger.
　特許文献１及び２には、蒸散燃料を吸着する吸着材と温度に応じて潜熱の吸収及び放出を生じる相変化物質をマイクロカプセルに封入した潜熱蓄熱材とを含むキャニスター用潜熱蓄熱型吸着材が提案されている。この吸着材によれば、吸脱着時の温度制御により従来のものに比べ、蒸散燃料の吸着－脱離性能は格段に優れているため、小型で高性能な吸着塔やキャニスターを供給できるという利点がある。 Patent Documents 1 and 2 describe a latent heat storage type adsorbent for canisters, which includes an adsorbent that adsorbs vaporized fuel and a latent heat storage material in which a phase change substance that absorbs and releases latent heat depending on the temperature is encapsulated in microcapsules. Proposed. According to this adsorbent, the adsorption-desorption performance of the transpired fuel is significantly superior to that of the conventional one due to the temperature control during adsorption and desorption, so there is an advantage that a small and high-performance adsorption tower and canister can be supplied. There is.
特開２０１０－１７９３０３号公報Japanese Unexamined Patent Publication No. 2010-179303 特開２００６－０６８６９３号公報Japanese Unexamined Patent Publication No. 2006-06693
　吸脱着性能を長期間にわたり高レベルで保持するためには溶剤蒸気への耐久性が重要となる。潜熱蓄熱材と活性炭を一体化させる製造過程において、潜熱蓄熱材の表面に物理的な損傷を与えてしまい、ＶＯＣ蒸気に晒されると潜熱蓄熱材を構成するマイクロカプセル内の潜熱物質が漏れ出てしまい、潜熱蓄熱材の熱量の低下、及び活性炭の細孔閉塞により本来の吸着材の性能を引き出せない。 Durability against solvent vapor is important to maintain high level of adsorption / desorption performance for a long period of time. In the manufacturing process of integrating the latent heat storage material and the activated charcoal, the surface of the latent heat storage material is physically damaged, and when exposed to VOC steam, the latent heat substance in the microcapsules constituting the latent heat storage material leaks out. Therefore, the original performance of the adsorbent cannot be brought out due to the decrease in the amount of heat of the latent heat storage material and the blockage of the pores of the activated charcoal.
　従って、本発明の目的は、上記欠点に鑑み、潜熱蓄熱材に損傷を与えることを抑制しつつ潜熱蓄熱材と活性炭とを一体化させ、潜熱蓄熱材と活性炭のペレットとを単に混合するよりも粒間空隙での伝熱ロスを防ぐことができ、効果的に吸着熱等を制御することで吸脱着性能、耐久性を高いレベルで維持できる吸着材を提供することにある。 Therefore, in view of the above drawbacks, an object of the present invention is to integrate the latent heat storage material and the activated carbon while suppressing damage to the latent heat storage material, rather than simply mixing the latent heat storage material and the pellets of the activated carbon. It is an object of the present invention to provide an adsorbent which can prevent heat transfer loss in intergranular voids and can maintain a high level of adsorption / desorption performance and durability by effectively controlling the heat of adsorption.
　本発明者らは、上記課題を解決するために鋭意研究を行った結果、相変化物質を封入したマイクロカプセルの表面を、熱硬化性有機バインダーＡを含む有機バインダー含有層で被覆し、さらに、活性炭を含む活性炭含有層で被覆することで、吸脱着性能、耐久性を高いレベルで維持できる吸着材が得られることを見出した。本発明者らは、このような知見に基づきさらに研究を重ね、本発明を完成させた。即ち、本発明は、以下の構成を包含する。 As a result of diligent research to solve the above problems, the present inventors coated the surface of the microcapsules containing the phase-changing substance with an organic binder-containing layer containing a thermosetting organic binder A, and further. It has been found that by coating with an activated carbon-containing layer containing activated carbon, an adsorbent capable of maintaining a high level of adsorption / desorption performance and durability can be obtained. Based on such findings, the present inventors have further studied and completed the present invention. That is, the present invention includes the following configurations.
　項１．温度に応じて潜熱の吸収及び放出を生じる相変化物
質を封入したマイクロカプセルを有する潜熱蓄熱材と、活性炭とを含有する潜熱蓄熱材一体型活性炭であって、
前記潜熱蓄熱材は、前記マイクロカプセルの表面が熱硬化性有機バインダーＡを含む有機バインダー含有層で被覆されており、且つ、
前記潜熱蓄熱材の表面が活性炭を含む活性炭含有層で被覆されている、潜熱蓄熱材一体型活性炭。 Item 1. A latent heat storage material integrated activated carbon containing microcapsules containing a phase-changing substance that absorbs and releases latent heat depending on the temperature and activated carbon.
In the latent heat storage material, the surface of the microcapsules is coated with an organic binder-containing layer containing a thermosetting organic binder A, and the latent heat storage material is coated with an organic binder-containing layer.
An activated carbon integrated with a latent heat storage material in which the surface of the latent heat storage material is coated with an activated carbon-containing layer containing activated carbon.
　項２．前記マイクロカプセルの平均粒子径が０．１～５００μｍである、項１に記載の潜熱蓄熱材一体型活性炭。 Item 2. Item 2. The latent heat storage material integrated activated carbon according to Item 1, wherein the microcapsules have an average particle size of 0.1 to 500 μm.
　項３．前記活性炭の平均粒子径が１μｍ～１０ｍｍである、項１又は２に記載の潜熱蓄熱材一体型活性炭。 Item 3. Item 2. The latent heat storage material integrated activated carbon according to Item 1 or 2, wherein the activated carbon has an average particle size of 1 μm to 10 mm.
　項４．前記活性炭含有層が、さらに、有機バインダーＢを含有する、項１～３のいずれか１項に記載の潜熱蓄熱材一体型活性炭。 Item 4. Item 2. The latent heat storage material integrated activated carbon according to any one of Items 1 to 3, wherein the activated carbon-containing layer further contains an organic binder B.
　項５．ＪＩＳ　Ｋ　１４７４（２０１４）に準拠して測定した、前記活性炭含有層の水懸濁液のｐＨが４．５以上である、項１～４のいずれか１項に記載の潜熱蓄熱材一体型活性炭。 Item 5. Item 2. The latent heat storage material integrated activated carbon according to any one of Items 1 to 4, wherein the pH of the aqueous suspension of the activated carbon-containing layer measured in accordance with JIS K 1474 (2014) is 4.5 or more. ..
　項６．前記潜熱蓄熱材の平均断面直径が０．７５～１．８０ｍｍである、項１～５のいずれか１項に記載の潜熱蓄熱材一体型活性炭。 Item 6. Item 2. The latent heat storage material integrated activated carbon according to any one of Items 1 to 5, wherein the latent heat storage material has an average cross-sectional diameter of 0.75 to 1.80 mm.
　項７．前記潜熱蓄熱材の含有量が、前記潜熱蓄熱材一体型活性炭の総量を１００質量％として、７～３０質量％である、項１～６のいずれか１項に記載の潜熱蓄熱材一体型活性炭。 Item 7. Item 2. The latent heat storage material integrated activated carbon according to any one of Items 1 to 6, wherein the content of the latent heat storage material is 7 to 30% by mass, where the total amount of the latent heat storage material integrated activated carbon is 100% by mass. ..
　項８．熱量が１０～１００Ｊ／ｇである、項１～７のいずれか１項に記載の潜熱蓄熱材一体型活性炭。 Item 8. Item 2. The latent heat storage material integrated activated carbon according to any one of Items 1 to 7, which has a calorific value of 10 to 100 J / g.
　項９．ＡＳＴＭ硬さが４５％以上である、項１～８のいずれか１項に記載の潜熱蓄熱材一体型活性炭。 Item 9. Item 2. The latent heat storage material integrated activated carbon according to any one of Items 1 to 8, which has an ASTM hardness of 45% or more.
　項１０．項１～９のいずれか１項に記載の潜熱蓄熱材一体型活性炭の製造方法であって、
（１）前記マイクロカプセルと前記熱硬化性有機バインダーＡとを混合する工程
（２）工程（１）で得られたマイクロカプセル組成物を前記熱硬化性有機バインダーＡで被覆し、熱処理して前記潜熱蓄熱材を得る工程、
（３）工程（２）で得られた潜熱蓄熱材と、前記活性炭を含む組成物とを混合して造粒する工程
を備える、製造方法。 Item 10. Item 2. The method for producing a latent heat storage material-integrated activated carbon according to any one of Items 1 to 9.
(1) Step of mixing the microcapsules and the thermosetting organic binder A (2) The microcapsule composition obtained in step (1) is coated with the thermosetting organic binder A and heat-treated to obtain the above. The process of obtaining latent heat storage material,
(3) A production method comprising a step of mixing and granulating the latent heat storage material obtained in the step (2) and the composition containing the activated carbon.
　項１１．前記工程（１）が、前記マイクロカプセルと前記熱硬化性有機バインダーＡとを混合後に押出造粒し、次いで整粒する工程である、項１０に記載の製造方法。 Item 11. Item 10. The production method according to Item 10, wherein the step (1) is a step of mixing the microcapsules and the thermosetting organic binder A, then extruding and granulating, and then sizing.
　項１２．前記工程（３）において、前記活性炭を含む組成物が、さらに、前記有機バインダーＢを含有する、項１０又は１１に記載の製造方法。 Item 12. Item 10. The production method according to Item 10 or 11, wherein in the step (3), the composition containing the activated carbon further contains the organic binder B.
　項１３．工程（３）において、前記活性炭を含む組成物が、さらに、ｐＨ調整剤を含有する、項１０～１２のいずれか１項に記載の製造方法。 Item 13. Item 8. The production method according to any one of Items 10 to 12, wherein in the step (3), the composition containing the activated carbon further contains a pH adjuster.
　項１４．項１～９のいずれか１項に記載の潜熱蓄熱材一体型活性炭を含有する、自動車用キャニスター。 Item 14. An automobile canister containing the latent heat storage material integrated activated carbon according to any one of Items 1 to 9.
　項１５．項１～９のいずれか１項に記載の潜熱蓄熱材一体型活性炭を含有する、密閉式ガソリンタンクと連結されている自動車用キャニスター。 Item 15. An automobile canister connected to a closed gasoline tank containing the latent heat storage material integrated activated carbon according to any one of Items 1 to 9.
　本発明によれば、吸脱着性能、耐久性を高いレベルで維持できる潜熱蓄熱材一体型活性炭を提供することができる。 According to the present invention, it is possible to provide an activated carbon with a latent heat storage material that can maintain a high level of adsorption / desorption performance and durability.
試験例１を実施後の熱硬化性有機バインダーでコーティングした潜熱蓄熱材一体型活性炭（実施例４）中の潜熱蓄熱材のＳＥＭ画像である。It is an SEM image of the latent heat storage material in the latent heat storage material integrated activated carbon (Example 4) coated with the thermosetting organic binder after carrying out Test Example 1. 試験例１を実施後の熱硬化性有機バインダーでコーティングしない潜熱蓄熱材一体型活性炭（比較例３）中の潜熱蓄熱材のＳＥＭ画像である。It is an SEM image of the latent heat storage material in the latent heat storage material integrated activated carbon (Comparative Example 3) which is not coated with the thermosetting organic binder after carrying out Test Example 1.
　本明細書において、「含有」は、「含む（comprise）」、「実質的にのみからなる（consist essentially of）」、及び「のみからなる（consist of）」のいずれも包含する概念である。また、本明細書において、数値範囲を「Ａ～Ｂ」で示す場合、Ａ以上Ｂ以下を意味する。 In the present specification, "contains" is a concept that includes any of "comprise", "consist essentially of", and "consist of". Further, in the present specification, when the numerical range is indicated by "A to B", it means A or more and B or less.
　１．潜熱蓄熱材一体型活性炭
　本発明の潜熱蓄熱材一体型活性炭は、温度に応じて潜熱の吸収及び放出を生じる相変化物質を封入したマイクロカプセルを有する潜熱蓄熱材と、活性炭とを含有する潜熱蓄熱材一体型活性炭であって、前記潜熱蓄熱材は、前記マイクロカプセルの表面が熱硬化性有機バインダーＡを含む有機バインダー含有層で被覆されており、且つ、前記潜熱蓄熱材の表面が活性炭を含む活性炭含有層で被覆されている。 1. 1. Latent heat storage material integrated activated charcoal The latent heat storage material integrated activated charcoal of the present invention contains a latent heat storage material having microcapsules encapsulating a phase change substance that absorbs and releases latent heat depending on the temperature, and an activated charcoal. In the material-integrated activated charcoal, the surface of the microcapsule is coated with an organic binder-containing layer containing a thermosetting organic binder A, and the surface of the latent heat storage material contains activated charcoal. It is coated with an activated charcoal-containing layer.
　このような構成を有する潜熱蓄熱材一体型活性炭は、潜熱蓄熱材への物理的なダメージなく製造することができるため、溶剤で晒された際に、潜熱蓄熱材からの内包物の溶出が抑制され長期にわたって安定し、且つその構造としては潜熱蓄熱材一つの表面に活性炭がコーティングされており、吸着熱による温度上昇を潜熱蓄熱材で効率よく抑制できるため高い溶剤吸脱着性能を示す。 Since the latent heat storage material integrated activated charcoal having such a configuration can be produced without physical damage to the latent heat storage material, elution of inclusions from the latent heat storage material is suppressed when exposed to a solvent. It is stable for a long period of time, and its structure is such that the surface of one latent heat storage material is coated with activated charcoal, and the temperature rise due to heat of adsorption can be efficiently suppressed by the latent heat storage material, so that it exhibits high solvent absorption / desorption performance.
　（１－１）マイクロカプセル
　マイクロカプセルに封入される相変化物質としては、相変化に伴って潜熱の吸収及び放出を生じ得る化合物であれば特に限定はない。相変化としては、例えば、固体－液体間の相変化等を例示することができる。相変化物質が相変化を生じ得る温度（例えば、融点、凝固点等）はキャニスターの用途に応じて適宜選択することができるが、通常０～５０℃程度とすることができる。 (1-1) Microcapsules The phase-changing substance encapsulated in the microcapsules is not particularly limited as long as it is a compound capable of absorbing and releasing latent heat as the phase changes. As the phase change, for example, a phase change between a solid and a liquid can be exemplified. The temperature at which the phase-changing substance can undergo a phase change (for example, melting point, freezing point, etc.) can be appropriately selected depending on the use of the canister, but is usually about 0 to 50 ° C.
　このような相変化物質として、好ましい化合物としては、例えば、テトラデカン、ペンタデカン、ヘキサデカン、ヘプタデカン、オクタデカン、ノナデカン、エイコサン、ドコサン等の直鎖の脂肪族炭化水素；天然ワックス；石油ワックス；ＬｉＮＯ３・３Ｈ２Ｏ、Ｎａ２ＳＯ４・１０Ｈ２Ｏ、Ｎａ２ＨＰＯ４・１２Ｈ２Ｏ等の無機化合物の水和物；カプリン酸、ラウリン酸等の脂肪酸；炭素数が１２～１５の高級アルコール；パルミチン酸メチル、ステアリン酸メチル等のエステル化合物等が挙げられる。相変化物質は、単独で用いることもできるし、融点を調整することを目的に２種以上を組合せて用いることもできる。２種以上の相変化物質を併用する場合、各相変化物質の相変化を生じる温度の差が、０～１５℃程度となるような組合せが好ましい。 Such phase change material, preferred compounds, for example, tetradecane, pentadecane, hexadecane, heptadecane, octadecane, nonadecane, eicosane, aliphatic hydrocarbon straight, such as docosane, natural wax; petroleum waxes; LiNO 3 · 3H Hydrate of inorganic compounds such as 2 O, Na 2 SO 4・ 10H 2 O, Na 2 HPO 4・ 12H 2 O; Fatty acids such as capric acid and lauric acid; Higher alcohols having 12 to 15 carbon atoms; Palmitic acid Examples thereof include ester compounds such as methyl and methyl stearate. The phase change substance can be used alone or in combination of two or more for the purpose of adjusting the melting point. When two or more kinds of phase-changing substances are used in combination, a combination is preferable in which the difference in temperature at which the phase-changing substances of each phase-changing substance occurs is about 0 to 15 ° C.
　また、場合によっては、相変化物質の過冷却現象を防止する為に、その相変化物質の融点より高融点の化合物を含有することもできる。 In some cases, in order to prevent the supercooling phenomenon of the phase-changing substance, a compound having a melting point higher than the melting point of the phase-changing substance can be contained.
　高融点化合物の具体的例としては、例えば、芳香族化合物、エステル類、カルボン酸類、アルコール類、アマイド類等が挙げられる。高融点化合物は、単独で用いることもでき、２種以上を組合せて用いることもできる。 Specific examples of the refractory compound include aromatic compounds, esters, carboxylic acids, alcohols, amides and the like. The refractory compound may be used alone or in combination of two or more.
　芳香族化合物としては、例えば、ハロゲン置換ベンゼン、ナフタレン等を例示できる。ハロゲン置換ベンゼンとしては、例えば、ジブロモベンゼン、ジクロロベンゼン等のジハロゲン化ベンゼンを例示できる。 Examples of the aromatic compound include halogen-substituted benzene and naphthalene. Examples of the halogen-substituted benzene include dihalogenated benzene such as dibromobenzene and dichlorobenzene.
　エステル類としては、例えば、メチルエイコサン酸等のモノアルコールの脂肪酸エステル；リノール酸グリセリド等のグリセリンの脂肪酸エステル等を例示できる。 Examples of the esters include fatty acid esters of monoalcohols such as methyleicosanoic acid; fatty acid esters of glycerin such as linoleic acid glyceride.
　カルボン酸類としては、例えば、ミリスチン酸、ペンタデシル酸、パルミチン酸、マルガリン酸、ステアリン酸、ノナデシル酸、エイコサン酸、ヘンイコサン酸、ベヘン酸等の脂肪族カルボン酸；安息香酸等の芳香族カルボン酸等を例示できる。 Examples of the carboxylic acids include aliphatic carboxylic acids such as myristic acid, pentadecylic acid, palmitic acid, margaric acid, stearic acid, nonadesyl acid, eicosanoic acid, henicosanoic acid and bechenic acid; and aromatic carboxylic acids such as benzoic acid. It can be exemplified.
　アルコール類としては、例えば、セチルアルコール、ヘプタデカノール、ステアリルアルコール、ノナデカノール、エイコサノール等の炭素数１６～３０のモノアルコール等を例示できる。 Examples of alcohols include monoalcohols having 16 to 30 carbon atoms such as cetyl alcohol, heptadecanol, stearyl alcohol, nonadecanol, and eikosanol.
　アマイド類としては、例えば、エイコサン酸アマイド、ノナデシル酸アマイド、ステアリン酸アマイド、オレイン酸アマイド等の脂肪酸アマイド等を例示できる。 Examples of amides include fatty acid amides such as icosane acid amide, nonadecylic acid amide, stearic acid amide, and oleic acid amide.
　高融点化合物を含有させる場合、その含有量は、溶剤吸脱着性能の観点から、相変化物質の含有量１００質量部に対して、０．５～３０質量部が好ましく、１～１５質量部がより好ましい。 When a refractory compound is contained, the content thereof is preferably 0.5 to 30 parts by mass and 1 to 15 parts by mass with respect to 100 parts by mass of the content of the phase change substance from the viewpoint of solvent adsorption / desorption performance. More preferred.
　マイクロカプセルの材料としては、公知の材料を用いることができ、例えば、樹脂等の高分子化合物を例示できる。高分子化合物としては、ホルムアルデヒド－メラミン樹脂、メラミン樹脂、ホルムアルデヒド－尿素樹脂、尿素樹脂、尿素－ホルムアルデヒド－ポリアクリル酸共重合体、ポリスチレン、ポリ酢酸ビニル、ポリアクリロニトリル、ポリエチレン、ポリブチルメタクリレート、ゼラチン等を例示できる。これらの材料は、単独で用いることもでき、２種以上を組合せて用いることもできる。 As the material of the microcapsules, a known material can be used, and for example, a polymer compound such as a resin can be exemplified. Examples of the polymer compound include formaldehyde-melamine resin, melamine resin, formaldehyde-urea resin, urea resin, urea-formaldehyde-polyacrylic acid copolymer, polystyrene, polyvinyl acetate, polyacrylonitrile, polyethylene, polybutyl methacrylate, gelatin and the like. Can be exemplified. These materials can be used alone or in combination of two or more.
　マイクロカプセルの材料と相変化物質の重量比は特に限定はないが、マイクロカプセルの材料と相変化物質との合計量を１００質量％として、溶剤吸脱着性能の観点から、通常、マイクロカプセルの材料の含有量は１０～３０質量％とすることができ、相変化物質の含有量は７０～９０質量％とすることができる。高融点化合物を使用する場合には、マイクロカプセルの材料と相変化物質と高融点化合物との合計量を１００質量％として、溶剤吸脱着性能の観点から、通常、マイクロカプセルの材料の含有量は１０～３０質量％とすることができ、相変化物質及び高融点化合物の合計含有量は７０～９０質量％とすることができる。 The weight ratio of the microcapsule material to the phase-changing substance is not particularly limited, but the total amount of the microcapsule material and the phase-changing substance is 100% by mass, and from the viewpoint of solvent adsorption / desorption performance, the material of the microcapsule is usually used. The content of the phase changing substance can be 10 to 30% by mass, and the content of the phase changing substance can be 70 to 90% by mass. When a high melting point compound is used, the total amount of the microcapsule material, the phase change substance, and the high melting point compound is set to 100% by mass, and the content of the microcapsule material is usually set from the viewpoint of solvent adsorption / desorption performance. It can be 10 to 30% by mass, and the total content of the phase change substance and the refractory compound can be 70 to 90% by mass.
　本発明において用いられる相変化物質をマイクロカプセル化する手法は、コアセルベーション法、界面重合法、ｉｎ－ｓｉｔｕ法、酵母菌を用いた手法等既存技術を用いることが可能であり、いずれの手法においても本発明の効果は達成させ得る。 As the method for microencapsulating the phase-changing substance used in the present invention, existing techniques such as a core selvation method, an interfacial polymerization method, an in-situ method, and a method using yeast can be used, and any of the methods can be used. However, the effect of the present invention can be achieved.
　例えば、相変化物質（及び必要に応じて高融点化合物）を液状媒体中で乳化剤等を用いて乳化し、これに所望の樹脂に対応する初期縮合物（プレポリマー）を添加した後、昇温し、重合反応を進めることにより、樹脂壁を有し相変化物質（及び必要に応じて高融点化合物）を含有するマイクロカプセル分散液（スラリー）を調製することができる。 For example, a phase change substance (and a refractory compound if necessary) is emulsified in a liquid medium using an emulsifier or the like, an initial condensate (prepolymer) corresponding to the desired resin is added thereto, and then the temperature is raised. Then, by advancing the polymerization reaction, a microcapsule dispersion (slurry) having a resin wall and containing a phase change substance (and a refractory compound if necessary) can be prepared.
　液状媒体としては、水が特に好ましいが、メタノール、エタノール、プロパノール等のアルコール、アセトン等の水混和性の溶媒も使用できる。上記溶媒は、単独で用いることもでき、２種以上を組合せて用いることもできる。 Water is particularly preferable as the liquid medium, but alcohols such as methanol, ethanol and propanol, and water-miscible solvents such as acetone can also be used. The above solvent may be used alone or in combination of two or more.
　マイクロカプセルの形状は、通常球形の粒子（粉末状又は顆粒状）であり、該粒子の粒径のコントロールは、カプセル化する際の乳化剤の種類と濃度、乳化時の温度及び時間、乳化方法等の因子により変動するため、実験により最適な条件が設定され得る。マイクロカプセルの平均粒子径は、具体的には、０．１～５００μｍ程度が好ましく、１～１００μｍ程度がより好ましく、２～１０μｍ程度がさらに好ましい。なお、マイクロカプセルの平均粒子径は、レーザー回折式粒子径分布測定装置（マイクロトラックベル製：マイクロトラックＭＴ３３００ＥＸＩＩ）により測定し、体積基準の累積５０％時の粒子径を平均粒子径とした。測定サンプルは、超音波を３０ｍin照射し二次粒子を解粒し1次粒子にしたものとする。 The shape of the microcapsules is usually spherical particles (powder or granules), and the particle size of the particles is controlled by the type and concentration of the emulsifier at the time of encapsulation, the temperature and time at the time of emulsification, the emulsification method, etc. Since it varies depending on the factors of, the optimum conditions can be set by experiments. Specifically, the average particle size of the microcapsules is preferably about 0.1 to 500 μm, more preferably about 1 to 100 μm, and even more preferably about 2 to 10 μm. The average particle size of the microcapsules was measured by a laser diffraction type particle size distribution measuring device (manufactured by Microtrac Bell: Microtrac MT3300EXII), and the particle size when the cumulative volume of the volume standard was 50% was taken as the average particle size. The measurement sample shall be obtained by irradiating 30 min of ultrasonic waves to crush the secondary particles into primary particles.
　（１－２）潜熱蓄熱材
　潜熱蓄熱材は、上記したマイクロカプセルの表面が熱硬化性有機バインダーＡを含む有機バインダー含有層で被覆されている。この際、熱硬化性有機バインダーＡを含む有機バインダー含有層で被覆されるマイクロカプセルの個数は特に制限はなく、１個でも複数（例えば２～１０個等）でもよいが、後述の本発明の製造方法によれば、通常、１個のマイクロカプセルが熱硬化性有機バインダーＡを含む有機バインダー含有層で被覆されることが多い。 (1-2) Latent Heat Storage Material In the latent heat storage material, the surface of the above-mentioned microcapsules is coated with an organic binder-containing layer containing a thermosetting organic binder A. At this time, the number of microcapsules coated with the organic binder-containing layer containing the thermosetting organic binder A is not particularly limited, and may be one or a plurality (for example, 2 to 10). According to the production method, one microcapsule is usually coated with an organic binder-containing layer containing a thermosetting organic binder A.
　熱硬化性有機バインダーＡとしては、一般的なものが使用でき特に限定はなく、例えば、フェノール樹脂、アクリル樹脂、エポキシ樹脂、イソシアネート樹脂、メラミン樹脂、ウレタン樹脂、アミドエステル樹脂等の熱硬化性樹脂が使用できる。そのうち、得られる潜熱蓄熱材のＪＩＳ硬さ（ＪＩＳ　Ｋ１４７４（２０１４））が高くなりやすい熱硬化性樹脂が好ましい。また、熱硬化性有機バインダーＡは、成型後において耐溶剤性（耐水性、耐有機溶剤性等）の高い樹脂が好ましい。 As the thermosetting organic binder A, a general one can be used and is not particularly limited. For example, a thermosetting resin such as a phenol resin, an acrylic resin, an epoxy resin, an isocyanate resin, a melamine resin, a urethane resin, or an amide ester resin is used. Can be used. Among them, a thermosetting resin in which the JIS hardness (JIS K1474 (2014)) of the obtained latent heat storage material tends to be high is preferable. Further, the thermosetting organic binder A is preferably a resin having high solvent resistance (water resistance, organic solvent resistance, etc.) after molding.
　上記のような耐溶剤性の高い熱硬化性有機バインダーＡを使用することにより、潜熱蓄熱材は後述の製造方法において使用できる溶剤によるマイクロカプセルの分散及び膨潤を防止しやすく、潜熱蓄熱材の硬さを維持しやすい。また、潜熱蓄熱材の硬さが高くなりやすいため、成型時の潜熱蓄熱材の粉化を抑制しやすいともに、活性炭による粉末状のマイクロカプセルの破壊を抑制しやすい。 By using the thermosetting organic binder A having high solvent resistance as described above, the latent heat storage material can easily prevent the dispersion and swelling of the microcapsules by the solvent that can be used in the production method described later, and the latent heat storage material is hard. Easy to maintain. Further, since the hardness of the latent heat storage material tends to be high, it is easy to suppress the pulverization of the latent heat storage material at the time of molding, and it is easy to suppress the destruction of powdered microcapsules by activated carbon.
　本発明において、潜熱蓄熱材中の熱硬化性有機バインダーＡの含有量は、活性炭の吸着熱による温度上昇を抑制しやすく、潜熱量を向上させやすく吸着性能を向上させやすいとともに耐久性も向上させやすい観点から、相変化物質を封入したマイクロカプセル１００質量部に対して５～２０質量部が好ましく、８～１８．５質量部がより好ましく、１４．５～１８.５質量部がさらに好ましい。 In the present invention, the content of the thermosetting organic binder A in the latent heat storage material easily suppresses the temperature rise due to the heat of adsorption of the activated charcoal, easily improves the amount of latent heat, improves the adsorption performance, and also improves the durability. From the viewpoint of ease, 5 to 20 parts by mass is preferable, 8 to 18.5 parts by mass is more preferable, and 14.5 to 18.5 parts by mass is further preferable with respect to 100 parts by mass of the microcapsule containing the phase change substance.
　本発明において、熱硬化性有機バインダーＡを含む有機バインダー含有層は、上記した熱硬化性有機バインダーＡのみから構成されていてもよいし、硬化促進剤、着色剤、可塑剤、安定剤、離型剤（ステアリン酸亜鉛等の金属石鹸）等の添加剤が含まれていてもよい。このような添加剤の含有量は、本発明の効果を損なわない範囲とすることが好ましく、有機バインダー含有層の総量を１００質量％として、０～１０質量％が好ましく、０～５質量％がより好ましく、０～３質量％がさらに好ましい。 In the present invention, the organic binder-containing layer containing the thermosetting organic binder A may be composed of only the above-mentioned thermosetting organic binder A, or may be a curing accelerator, a coloring agent, a plasticizing agent, a stabilizer, and a release agent. Additives such as a mold agent (metal soap such as zinc stearate) may be contained. The content of such an additive is preferably in a range that does not impair the effects of the present invention, and is preferably 0 to 10% by mass, preferably 0 to 5% by mass, with the total amount of the organic binder-containing layer being 100% by mass. More preferably, 0 to 3% by mass is further preferable.
　本発明において、有機バインダー含有層も含めた潜熱蓄熱材の形状は、特に制限はなく、ペレット状（円柱状、球状等）、ディスク状、ブロック状等のいずれも採用できる。 In the present invention, the shape of the latent heat storage material including the organic binder-containing layer is not particularly limited, and any of pellet shape (cylindrical shape, spherical shape, etc.), disk shape, block shape, etc. can be adopted.
　本発明において、有機バインダー含有層も含めた潜熱蓄熱材の平均断面直径は、特に制限されるわけではないが、活性炭の吸着熱による温度上昇を抑制しやすく、潜熱量を向上させやすく吸着性能を向上させやすいとともに耐久性も向上させやすい観点から、０．７５～１．８０ｍｍが好ましく、０．７８～１．５０ｍｍがより好ましく、０．８０～１．２０ｍｍがさらに好ましい。なお、成型機のダイス等の穴を通過させる場合は、マイクロカプセルの割れによる性能劣化を抑制しやすいため、当該穴よりも小さくすることが好ましい。また、潜熱蓄熱材の平均断面直径は、ノギスにより算出する。 In the present invention, the average cross-sectional diameter of the latent heat storage material including the organic binder-containing layer is not particularly limited, but it is easy to suppress the temperature rise due to the adsorption heat of the activated carbon, and it is easy to improve the latent heat amount to improve the adsorption performance. From the viewpoint of easy improvement and easy improvement of durability, 0.75 to 1.80 mm is preferable, 0.78 to 1.50 mm is more preferable, and 0.80 to 1.20 mm is further preferable. When passing through a hole such as a die of a molding machine, it is preferable to make the hole smaller than the hole because it is easy to suppress performance deterioration due to cracking of the microcapsules. The average cross-sectional diameter of the latent heat storage material is calculated by calipers.
　本発明において、潜熱蓄熱材一体型活性炭中の潜熱蓄熱材のＪＩＳ硬さは、潜熱蓄熱材と活性炭との接触による割れ及び微粉化を抑制しやすい観点から、本発明の潜熱蓄熱材一体型活性炭よりも大きいことが好ましい。具体的には、潜熱蓄熱材のＪＩＳ硬さは、例えば、９０％以上が好ましく、９５～１００％がより好ましい。潜熱蓄熱材のＪＩＳ硬さは、ＪＩＳ　Ｋ１４７４（２０１４）に準じ測定する。 In the present invention, the JIS hardness of the latent heat storage material-integrated activated carbon in the latent heat storage material-integrated activated carbon is from the viewpoint of easily suppressing cracking and pulverization due to contact between the latent heat storage material and the activated carbon, the latent heat storage material-integrated activated carbon of the present invention. Is preferably larger than. Specifically, the JIS hardness of the latent heat storage material is, for example, preferably 90% or more, and more preferably 95 to 100%. The JIS hardness of the latent heat storage material is measured according to JIS K1474 (2014).
　（１－３）潜熱蓄熱材一体型活性炭
　本発明の潜熱蓄熱材一体型活性炭は、上記したマイクロカプセルの表面に有機バインダー含有層を形成した潜熱蓄熱材の表面が、さらに、活性炭を含む活性炭含有層で被覆されている。この際、活性炭を含む活性炭含有層で被覆される潜熱蓄熱材の個数は特に制限はなく、１個でも複数（例えば２～１０個等）でもよいが、後述の本発明の製造方法によれば、通常、１個の潜熱蓄熱材が活性炭を含む活性炭含有層で被覆されることが多い。 (1-3) Latent heat storage material integrated activated carbon In the latent heat storage material integrated activated carbon of the present invention, the surface of the latent heat storage material having an organic binder-containing layer formed on the surface of the above-mentioned microcapsules further contains activated carbon containing activated carbon. It is covered with a layer. At this time, the number of latent heat storage materials coated with the activated carbon-containing layer containing activated carbon is not particularly limited and may be one or a plurality (for example, 2 to 10), but according to the production method of the present invention described later. Usually, one latent heat storage material is often coated with an activated carbon-containing layer containing activated carbon.
　本発明に使用される活性炭としては、一般的に使用されているキャニスター用の活性炭が使用できる。活性炭は、石炭系、ヤシガラ系、木質系、リグニン系等の種々の原料から得られるものを使用でき、水蒸気賦活品；炭酸ガス賦活品；リン酸、塩化亜鉛、アルカリ金属等による薬品賦活品等の活性炭の賦活品を使用できる。 As the activated carbon used in the present invention, a commonly used activated carbon for canisters can be used. As the activated carbon, those obtained from various raw materials such as coal-based, coconut shell-based, wood-based, and lignin-based can be used, and steam activated products; carbon dioxide gas activated products; chemical activated products using phosphoric acid, zinc chloride, alkali metals, etc. Activated carbon products can be used.
　また本発明に適用される活性炭は、粉末、粒状、破砕炭等の形態を問わないが、キャニスター用途に使用する場合は、蒸散燃料の吸着能を上げるため細孔を有する粉末状のものが好ましい。 The activated carbon applied to the present invention may be in any form such as powder, granular, crushed charcoal, etc., but when used for canister applications, it is preferably in the form of powder having pores in order to increase the adsorption capacity of the evaporated fuel. ..
　本発明において、活性炭粉末の平均粒子径は、特に制限されるわけではないが、活性炭の吸着熱による温度上昇を抑制しやすく、潜熱量を向上させやすく吸着性能を向上させやすいとともに耐久性も向上させやすい観点から、１μｍ～１０ｍｍが好ましく、５μｍ～１ｍｍがより好ましく、１０～１００μｍがさらに好ましい。なお、活性炭粉末の平均粒子径は、レーザー回折式粒子径分布測定装置（マイクロトラック・ベル製：マイクロトラックＭＴ３３００ＥＸＩＩ）により測定し、体積基準の累積５０％時の粒子径を平均粒子径とする。 In the present invention, the average particle size of the activated carbon powder is not particularly limited, but it is easy to suppress the temperature rise due to the adsorption heat of the activated carbon, it is easy to improve the latent heat amount, it is easy to improve the adsorption performance, and the durability is also improved. From the viewpoint of easy acclimation, 1 μm to 10 mm is preferable, 5 μm to 1 mm is more preferable, and 10 to 100 μm is further preferable. The average particle size of the activated carbon powder is measured by a laser diffraction type particle size distribution measuring device (Microtrac Bell: Microtrac MT3300EXII), and the average particle size is defined as a volume-based cumulative particle size of 50%.
　本発明において、活性炭の比表面積は、特に制限されるわけではないが、活性炭の吸着熱による温度上昇を抑制しやすく、潜熱量を向上させやすく吸着性能を向上させやすいとともに耐久性も向上させやすい観点から、５００～２５００ｍ２／ｇが好ましく、６００～２４００ｍ２／ｇがより好ましく、８００～２０００ｍ２／ｇがさらに好ましい。なお、直径３０ｎｍ以下の活性炭の比表面積は、比表面積／細孔分布測定装置（マイクロトラック・ベル（株）製：Ｂｅｌｓｏｒｐ　ｍｉｎｉＩＩ）により測定し、液体窒素温度での活性炭の窒素吸着等温線を作成し、Ｃｒａｎｓｔｏｎ－Ｉｎｋｌｅｙ（ＣＩ）法により算出する。 In the present invention, the specific surface area of the activated carbon is not particularly limited, but it is easy to suppress the temperature rise due to the heat of adsorption of the activated carbon, it is easy to improve the latent heat amount, it is easy to improve the adsorption performance, and it is easy to improve the durability. From the viewpoint, 500 to 2500 m 2 / g is preferable, 600 to 2400 m 2 / g is more preferable, and 800 to 2000 m 2 / g is further preferable. The specific surface area of activated carbon having a diameter of 30 nm or less is measured by a specific surface area / pore distribution measuring device (manufactured by Microtrac Bell Co., Ltd .: Belsorb miniII), and a nitrogen adsorption isotherm of activated carbon at liquid nitrogen temperature is created. Then, it is calculated by the Cranston-Inkley (CI) method.
　活性炭の細孔容積は、特に制限はなく、活性炭の吸着熱による温度上昇を抑制しやすく、潜熱量を向上させやすく吸着性能を向上させやすいとともに耐久性も向上させやすい観点から、例えば０．１０～１．００ｍＬ／ｇが好ましく、０．２０～０．９０ｍＬ／ｇがより好ましく、０．３０～０．８０ｍＬ／ｇがさらに好ましい。なお、直径３０ｎｍ以下の活性炭の細孔容積は、比表面積／細孔分布測定装置（マイクロトラック・ベル（株）製：Ｂｅｌｓｏｒｐ　ｍｉｎｉＩＩ）により測定し、液体窒素温度での活性炭の窒素吸着等温線を作成し、Ｃｒａｎｓｔｏｎ－Ｉｎｋｌｅｙ（ＣＩ）法により算出する。 The pore volume of the activated carbon is not particularly limited, and from the viewpoint that it is easy to suppress the temperature rise due to the adsorption heat of the activated carbon, it is easy to improve the latent heat amount, it is easy to improve the adsorption performance, and it is easy to improve the durability, for example, 0.10. It is preferably ~ 1.00 mL / g, more preferably 0.20 to 0.90 mL / g, and even more preferably 0.30 to 0.80 mL / g. The pore volume of activated carbon with a diameter of 30 nm or less is measured by a specific surface area / pore distribution measuring device (manufactured by Microtrac Bell Co., Ltd .: Belsolp miniII), and the nitrogen adsorption isotherm of activated carbon at liquid nitrogen temperature is measured. It is prepared and calculated by the Cranston-Inkley (CI) method.
　本発明において、活性炭のｐＨは、例えば、中性又は塩基性下ではカルボン酸塩の状態でありバインダーは水に溶けやすいため、活性炭表面のバインダーの均一性を向上させやすく、硬さを向上させやすい。このため、特に制限されるわけではないが、ＪＩＳ　Ｋ　１４７４（２０１４）に準拠して測定した、活性炭の水懸濁液のｐＨは、４．０以上が好ましく、４．５以上がより好ましく、５．０以上がさらに好ましい。なお、ＪＩＳ　Ｋ　１４７４（２０１４）に準拠して測定した、活性炭の水懸濁液のｐＨの上限値は特に制限はないが、通常、１４．０程度である。 In the present invention, the pH of the activated carbon is, for example, a carboxylate state under neutral or basic conditions, and the binder is easily dissolved in water. Therefore, the uniformity of the binder on the surface of the activated carbon is easily improved, and the hardness is improved. Cheap. Therefore, although not particularly limited, the pH of the aqueous suspension of activated carbon measured in accordance with JIS K 1474 (2014) is preferably 4.0 or higher, more preferably 4.5 or higher. 5.0 or more is more preferable. The upper limit of the pH of the aqueous suspension of activated carbon measured in accordance with JIS K 1474 (2014) is not particularly limited, but is usually about 14.0.
　本発明において、潜熱蓄熱材一体型活性炭中の潜熱蓄熱材の含有量は、温度変化量を抑制しやすく、潜熱量を向上させやすく吸着性能を向上させやすいとともに耐久性も向上させやすい観点から、潜熱蓄熱材一体型活性炭の総量を１００質量％として、７～３０質量％が好ましく、９～２９質量％がより好ましく、１４～１９質量％がさらに好ましい。 In the present invention, the content of the latent heat storage material in the latent heat storage material integrated activated coal is from the viewpoint that the amount of temperature change is easily suppressed, the latent heat amount is easily improved, the adsorption performance is easily improved, and the durability is also easily improved. When the total amount of the latent heat storage material integrated activated charcoal is 100% by mass, it is preferably 7 to 30% by mass, more preferably 9 to 29% by mass, still more preferably 14 to 19% by mass.
　本発明において、潜熱蓄熱材一体型活性炭中の活性炭の含有量は、温度変化量を抑制しやすく、潜熱量を向上させやすく吸着性能を向上させやすいとともに耐久性も向上させやすい観点から、潜熱蓄熱材一体型活性炭の総量を１００質量％として、６２～８６質量％が好ましく、６３～８４質量％がより好ましく、７３～７９質量％がさらに好ましい。 In the present invention, the content of activated carbon in the activated carbon integrated with the latent heat storage material is easy to suppress the amount of temperature change, easily improve the latent heat amount, improve the adsorption performance, and easily improve the durability. With the total amount of the material-integrated activated carbon as 100% by mass, 62 to 86% by mass is preferable, 63 to 84% by mass is more preferable, and 73 to 79% by mass is further preferable.
　本発明の潜熱蓄熱材一体型活性炭が有する活性炭含有層は、上記した活性炭のみから構成することもできるが、さらに、有機バインダーＢを含んでいてもよい。 The activated carbon-containing layer contained in the activated carbon integrated with the latent heat storage material of the present invention may be composed of only the above-mentioned activated carbon, but may further contain an organic binder B.
　有機バインダーＢとしては、一般的に活性炭等の吸着材の成型に使用されている熱可塑性樹脂又は熱硬化性樹脂のバインダーを使用することができる他、塗料・粘接着剤、繊維処理バインダー、フィルム等のコーティング剤の架橋・密着向上剤、熱可塑樹脂、添加剤を用いることができる。例えば、メチルセルロース、カルボキシルメチルセルロース等のセルロース誘導体、フェノール樹脂、メラミン樹脂、エポキシ樹脂、ウレタン樹脂、ポリビニルアルコール、酢酸ビニル、塩化ビニリデン樹脂、オキサゾリン含有ポリマー等の一般に使用されているものを制限なく使用できる。これらの有機バインダーＢは、単独で用いることもでき、２種以上を組合せて用いることもできる。また、上記した熱硬化性有機バインダーＡと同じものを使用してもよいし、異なるものを使用してもよい。 As the organic binder B, a binder of a thermoplastic resin or a thermosetting resin generally used for molding an adsorbent such as activated charcoal can be used, as well as a paint / adhesive, a fiber treatment binder, and the like. Cross-linking / adhesion improving agents, thermoplastic resins, and additives for coating agents such as films can be used. For example, commonly used ones such as cellulose derivatives such as methyl cellulose and carboxylmethyl cellulose, phenol resins, melamine resins, epoxy resins, urethane resins, polyvinyl alcohols, vinyl acetate, vinylidene chloride resins, and oxazoline-containing polymers can be used without limitation. These organic binders B can be used alone or in combination of two or more. Further, the same one as the above-mentioned thermosetting organic binder A may be used, or a different one may be used.
　本発明において、潜熱蓄熱材一体型活性炭中の有機バインダーＢの含有量は、活性炭の細孔を塞ぎにくく、温度変化量を抑制しやすく、潜熱量を向上させやすく吸着性能を向上させやすいとともに耐久性や硬さも向上させやすい観点から、潜熱蓄熱材一体型活性炭の総量を１００質量％として、５～１０質量％が好ましく、６～９質量％がより好ましく、７～８質量％がさらに好ましい。 In the present invention, the content of the organic binder B in the activated carbon integrated with the latent heat storage material makes it difficult to block the pores of the activated carbon, easily suppresses the amount of temperature change, easily improves the latent heat amount, and easily improves the adsorption performance and is durable. From the viewpoint of easily improving the properties and hardness, the total amount of the latent heat storage material integrated activated carbon is 100% by mass, preferably 5 to 10% by mass, more preferably 6 to 9% by mass, still more preferably 7 to 8% by mass.
　本発明の潜熱蓄熱材一体型活性炭が有する活性炭含有層は、上記した活性炭及び必要に応じて有機バインダーＢのみから構成することもできる。上記のとおり、中性又は塩基性下では、活性炭表面のバインダーの均一性を向上させやすく、硬さを向上させやすいため、ｐＨ調整剤によりｐＨを調整することができる。 The activated carbon-containing layer contained in the activated carbon integrated with the latent heat storage material of the present invention may be composed of only the above-mentioned activated carbon and, if necessary, the organic binder B. As described above, under neutral or basic conditions, the uniformity of the binder on the surface of the activated carbon is easily improved and the hardness is easily improved, so that the pH can be adjusted with a pH adjuster.
　ｐＨ調整剤は酸、塩基、塩、緩衝液等がいずれも使用できる。例えば、水酸化ナトリウム、水酸化カリウム、水酸化カリウム、水酸化バリウム、アンモニア、水酸化マグネシウム、水酸化カルシウム、水酸化アルミニウム等の塩基；塩酸、硝酸、リン酸、ホウ酸、酢酸、クエン酸、炭酸等の酸；炭酸水素ナトリウム、炭酸ナトリウム、酢酸ナトリウム、リン酸二水素ナトリウム、リン酸水素ナトリウム、硫酸水素ナトリウム等の塩；これらを組み合わせた緩衝液等が挙げられる。 Acid, base, salt, buffer solution, etc. can be used as the pH adjuster. For example, bases such as sodium hydroxide, potassium hydroxide, potassium hydroxide, barium hydroxide, ammonia, magnesium hydroxide, calcium hydroxide, aluminum hydroxide; hydrochloric acid, nitrate, phosphoric acid, boric acid, acetic acid, citric acid, Acids such as carbonic acid; salts such as sodium hydrogen carbonate, sodium carbonate, sodium acetate, sodium dihydrogen phosphate, sodium hydrogen phosphate, sodium hydrogen sulfate and the like; buffer solutions combining these can be mentioned.
　本発明において、潜熱蓄熱材一体型活性炭中のｐＨ調整剤の含有量は、活性炭表面のバインダーの均一性を向上させやすく、硬さを向上させやすい観点から、潜熱蓄熱材一体型活性炭の総量を１００質量％として、０～１０質量％が好ましく、０～５質量％がより好ましい。 In the present invention, the content of the pH adjuster in the latent heat storage material integrated activated carbon is the total amount of the latent heat storage material integrated activated carbon from the viewpoint of easily improving the uniformity of the binder on the surface of the activated carbon and easily improving the hardness. As 100% by mass, 0 to 10% by mass is preferable, and 0 to 5% by mass is more preferable.
　本発明において、活性炭を含む活性炭含有層は、上記した活性炭及び必要に応じて有機バインダーＢのみから構成されていてもよいし、架橋剤、着色剤、可塑剤、安定剤、離型剤（ステアリン酸亜鉛等の金属石鹸）等の添加剤が含まれていてもよい。このような添加剤の含有量は、本発明の効果を損なわない範囲とすることが好ましく、活性炭含有層の総量を１００質量％として、０～１０質量％が好ましく、０～５質量％がより好ましく、０～３質量％がさらに好ましい。 In the present invention, the activated carbon-containing layer containing activated carbon may be composed of only the above-mentioned activated carbon and, if necessary, organic binder B, or a cross-linking agent, a coloring agent, a plasticizing agent, a stabilizer, and a mold release agent (stearic acid). Additives such as (metal soap such as zinc acid acid) may be contained. The content of such an additive is preferably in a range that does not impair the effects of the present invention, and is preferably 0 to 10% by mass, more preferably 0 to 5% by mass, with the total amount of the activated carbon-containing layer being 100% by mass. It is preferable, and 0 to 3% by mass is more preferable.
　本発明において、活性炭含有層のｐＨは、例えば、中性、塩基性下ではカルボン酸塩の状態であり水に溶けやすいため、活性炭表面のバインダーの均一性を向上させやすく、硬さを向上させやすい。このため、特に制限されるわけではないが、ＪＩＳ　Ｋ　１４７４（２０１４）に準拠して測定した、活性炭含有層の水懸濁液のｐＨは、４．５以上が好ましく、５．５以上がより好ましく、６．０以上がさらに好ましい。なお、ＪＩＳ　Ｋ　１４７４（２０１４）に準拠して測定した、活性炭含有層の水懸濁液のｐＨの上限値は特に制限はないが、通常、１４．０程度である。 In the present invention, the pH of the activated carbon-containing layer is, for example, in the state of a carboxylate under neutral and basic conditions and is easily dissolved in water, so that it is easy to improve the uniformity of the binder on the surface of the activated carbon and improve the hardness. Cheap. Therefore, although not particularly limited, the pH of the aqueous suspension of the activated carbon-containing layer measured in accordance with JIS K 1474 (2014) is preferably 4.5 or higher, more preferably 5.5 or higher. It is preferable, and 6.0 or more is more preferable. The upper limit of the pH of the aqueous suspension of the activated carbon-containing layer measured in accordance with JIS K 1474 (2014) is not particularly limited, but is usually about 14.0.
　本発明において、活性炭を含む活性炭含有層の厚みは、特に制限されるわけではないが、活性炭の吸着熱による温度上昇を抑制しやすく、潜熱量を向上させやすく吸着性能を向上させやすいとともに耐久性も向上させやすい観点から、１８０～２０５０μｍが好ましく、２５０～９００μｍがより好ましく、３５０～７８０μｍがさらに好ましい。なお、活性炭含有層の厚みは、一体炭を割り、蓄熱材を除去した後、ノギスにより測定する。 In the present invention, the thickness of the activated carbon-containing layer containing activated carbon is not particularly limited, but it is easy to suppress the temperature rise due to the heat of adsorption of the activated carbon, it is easy to improve the latent heat amount, and it is easy to improve the adsorption performance and durability. From the viewpoint of easy improvement, 180 to 2050 μm is preferable, 250 to 900 μm is more preferable, and 350 to 780 μm is further preferable. The thickness of the activated carbon-containing layer is measured with a caliper after breaking the monolithic coal and removing the heat storage material.
　上記した本発明の潜熱蓄熱材一体型活性炭の形状は特に制限されるわけではないが、例えば、後述の製造方法によれば、球状又は楕円球状となりやすい。 The shape of the latent heat storage material-integrated activated carbon of the present invention described above is not particularly limited, but for example, according to the manufacturing method described later, it tends to be spherical or elliptical spherical.
　本発明の潜熱蓄熱材一体型活性炭の平均粒子径は、特に制限されるわけではないが、活性炭の吸着熱による温度上昇を抑制しやすく、潜熱量を向上させやすく吸着性能を向上させやすいとともに耐久性も向上させやすく、通気抵抗を低くしやすく、キャニスター内での空気の流れを向上させやすい観点から、１．０～４．０ｍｍが好ましく、１．２～３．４ｍｍがより好ましく、１．７～２．８ｍｍがさらに好ましい。なお、本発明の潜熱蓄熱材一体型活性炭の平均粒子径はＪＩＳ　Ｋ１４７４（２０１４）に準じ、ロータップと篩を用いて篩別し、質量平均粒子径を算出する。 The average particle size of the activated carbon integrated with the latent heat storage material of the present invention is not particularly limited, but it is easy to suppress the temperature rise due to the adsorption heat of the activated carbon, it is easy to improve the latent heat amount, it is easy to improve the adsorption performance, and it is durable. From the viewpoint of easily improving the property, easily lowering the ventilation resistance, and easily improving the air flow in the canister, 1.0 to 4.0 mm is preferable, 1.2 to 3.4 mm is more preferable, and 1. 7 to 2.8 mm is more preferable. The average particle size of the latent heat storage material-integrated activated carbon of the present invention is sieved using a low tap and a sieve according to JIS K1474 (2014), and the mass average particle size is calculated.
　このようにして得られる本発明の潜熱蓄熱材一体型活性炭の熱量は、１０～１００Ｊ／ｇ、好ましくは１１～８０Ｊ／ｇ、より好ましくは１２～６０Ｊ／ｇとすることができる。このため、本発明の潜熱蓄熱材一体型活性炭は、活性炭の吸着熱による温度上昇を抑制しやすく、吸脱着性能や耐久性、硬さ等を向上させやすい。なお、潜熱蓄熱材の熱量は、ＤＳＣ７０２０（示差走査熱量計、セイコーインスツル（株）製）により測定する。 The calorific value of the latent heat storage material-integrated activated carbon of the present invention thus obtained can be 10 to 100 J / g, preferably 11 to 80 J / g, and more preferably 12 to 60 J / g. Therefore, the activated carbon integrated with the latent heat storage material of the present invention can easily suppress the temperature rise due to the heat of adsorption of the activated carbon, and can easily improve the adsorption / desorption performance, durability, hardness, and the like. The calorific value of the latent heat storage material is measured by DSC7020 (differential scanning calorimeter, manufactured by Seiko Instruments Inc.).
　本発明の潜熱蓄熱材一体型活性炭のｐＨは、例えば、中性、塩基性下ではカルボン酸塩の状態であり水に溶けやすいため、活性炭表面のバインダーの均一性を向上させやすく、硬さを向上させやすい。このため、特に制限されるわけではないが、ＪＩＳ　Ｋ　１４７４（２０１４）に準拠して測定した、本発明の潜熱蓄熱材一体型活性炭の水懸濁液のｐＨは、４．５以上が好ましく、５．５以上がより好ましく、６．０以上がさらに好ましい。なお、ＪＩＳ　Ｋ　１４７４（２０１４）に準拠して測定した、本発明の潜熱蓄熱材一体型活性炭の水懸濁液のｐＨの上限値は特に制限はないが、通常、１４．０程度である。 The pH of the activated carbon integrated with the latent heat storage material of the present invention is, for example, in the state of a carboxylic acid salt under neutral and basic conditions and is easily dissolved in water. Easy to improve. Therefore, although not particularly limited, the pH of the aqueous suspension of the latent heat storage material-integrated activated carbon of the present invention measured in accordance with JIS K 1474 (2014) is preferably 4.5 or more. 5.5 or more is more preferable, and 6.0 or more is further preferable. The upper limit of the pH of the aqueous suspension of the latent heat storage material-integrated activated carbon of the present invention measured in accordance with JIS K 1474 (2014) is not particularly limited, but is usually about 14.0.
　このようにして得られる本発明の潜熱蓄熱材一体型活性炭は、硬さを高くすることができる。具体的には、本発明の潜熱蓄熱材一体型活性炭のＡＳＴＭ硬さは、４５％以上が好ましく、４８～８０％がより好ましく、５０～８０％がさらに好ましい。本発明の潜熱蓄熱材一体型活性炭のＡＳＴＭ硬さは、ＡＳＴＭ－Ｄ５２２８に準拠して測定する。 The latent heat storage material integrated activated carbon of the present invention thus obtained can have a high hardness. Specifically, the ASTM hardness of the latent heat storage material-integrated activated carbon of the present invention is preferably 45% or more, more preferably 48 to 80%, and even more preferably 50 to 80%. The ASTM hardness of the latent heat storage material integrated activated carbon of the present invention is measured according to ASTM-D5228.
　このようにして得られる本発明の潜熱蓄熱材一体型活性炭は、燃料蒸散ガス吸着性能を表すブタンアクティビティ（ＢＡ）を高くすることができる。具体的には、本発明の潜熱蓄熱材一体型活性炭のブタンアクティビティ（ＢＡ）は、４２％以上が好ましく、４３～６０％がより好ましく、４４～５３％がさらに好ましい。なお、ブタンアクティビティ（ＢＡ）が４２％以上であれば、燃料蒸散ガス吸着性能に優れていることが知られている。本発明の潜熱蓄熱材一体型活性炭のブタンアクティビティ（ＢＡ）は、ＡＳＴＭ－Ｄ５２２８に準拠して測定する。 The latent heat storage material-integrated activated carbon of the present invention thus obtained can increase the butane activity (BA) indicating the fuel evaporation gas adsorption performance. Specifically, the butane activity (BA) of the latent heat storage material-integrated activated carbon of the present invention is preferably 42% or more, more preferably 43 to 60%, still more preferably 44 to 53%. It is known that when butane activity (BA) is 42% or more, the fuel evaporation gas adsorption performance is excellent. The butane activity (BA) of the latent heat storage material-integrated activated carbon of the present invention is measured according to ASTM-D5228.
　以上のような本発明の潜熱蓄熱材一体型活性炭は、キャニスターの容器に充填し、該容器に燃料タンクからの蒸散燃料ガスを導入することでキャニスターを構成し、蒸散燃料ガスを吸着させることができる。燃料タンクで発生する蒸発燃料を吸着するキャニスターに特に制限されるものではなく、既存のものが使用できる。たとえば自動車用途としては密閉式燃料タンクや通常の燃料タンクに連結したキャニスター等がある。なお、密閉式燃料タンクや通常の燃料タンクとキャニスターの連結は、直接的に接続することも、その間に封鎖弁や開放弁を介して間接的に接続することもできる。 The latent heat storage material-integrated activated charcoal of the present invention as described above can be filled in a canister container, and the vaporized fuel gas from the fuel tank is introduced into the container to form a canister and adsorb the vaporized fuel gas. can. The canister that adsorbs the evaporated fuel generated in the fuel tank is not particularly limited, and an existing one can be used. For example, automobile applications include closed fuel tanks and canisters connected to ordinary fuel tanks. The connection between the closed fuel tank or the normal fuel tank and the canister can be directly connected or indirectly connected via a blocking valve or an opening valve between them.
　ガス及び容器の温度は、相変化物質の相変化温度（通常は融点）以下であることが好ましい。つまり、本発明の潜熱蓄熱材一体型活性炭は、キャニスター用潜熱蓄熱材一体型活性炭として有用である。 The temperature of the gas and the container is preferably equal to or lower than the phase change temperature (usually the melting point) of the phase change substance. That is, the latent heat storage material integrated activated carbon of the present invention is useful as a latent heat storage material integrated activated carbon for canisters.
　本発明の潜熱蓄熱材一体型球状活性炭が適用できる蒸散燃料ガスとしては、例えば、溶剤回収で多用される炭化水素系やケトン、ハロゲン系、アルコール、エステルや自動車用ガソリン等が挙げられる。 Examples of the vaporized fuel gas to which the latent heat storage material-integrated spherical activated carbon of the present invention can be applied include hydrocarbon-based, ketone, halogen-based, alcohol, ester, and gasoline for automobiles, which are often used in solvent recovery.
　２．潜熱蓄熱材一体型活性炭の製造方法
　本発明の潜熱蓄熱材一体型活性炭の製造方法は、特に制限されないが、例えば、
（１）前記マイクロカプセルと前記熱硬化性有機バインダーＡとを混合する工程
（２）工程（１）で得られたマイクロカプセル組成物を前記熱硬化性有機バインダーＡで被覆し、熱処理して前記潜熱蓄熱材を得る工程、
（３）工程（２）で得られた潜熱蓄熱材と、前記活性炭を含む組成物とを混合して造粒する工程
を備える方法により製造することができる。 2. Method for Producing Activated Carbon Integrated with Latent Heat Storage Material The method for producing activated carbon integrated with latent heat storage material of the present invention is not particularly limited, but for example.
(1) Step of mixing the microcapsules and the thermosetting organic binder A (2) The microcapsule composition obtained in step (1) is coated with the thermosetting organic binder A and heat-treated to obtain the above. The process of obtaining latent heat storage material,
(3) It can be produced by a method including a step of mixing and granulating the latent heat storage material obtained in the step (2) and the composition containing the activated carbon.
　（２－１）工程（１）
　工程（１）では、まず、マイクロカプセルと熱硬化性有機バインダーＡとを混合する。具体的には、工程（１）では、マイクロカプセルと熱硬化性有機バインダーＡとを混合後に押出造粒し、次いで整粒することが好ましい。この際の熱硬化性有機バインダーＡは、マイクロカプセルの表面にコーティングするものではなく、マイクロカプセルと混合するために使用される。 (2-1) Step (1)
In the step (1), first, the microcapsules and the thermosetting organic binder A are mixed. Specifically, in step (1), it is preferable that the microcapsules and the thermosetting organic binder A are mixed, then extruded and granulated, and then granulated. The thermosetting organic binder A at this time is not coated on the surface of the microcapsules, but is used for mixing with the microcapsules.
　本発明において、熱硬化性有機バインダーＡの添加量は、工程（２）で得られる潜熱蓄熱材の結着力を向上させやすくして硬さ及び耐溶剤性を向上させやすくマイクロカプセルが破壊されにくいとともに、潜熱量を向上させやすく吸着性能を向上させやすく、混合時の分散性を向上させて材料のムラを抑制しやすい観点から、マイクロカプセル１００質量部に対して５～３０質量部が好ましく、８～２５質量部がより好ましく、１０～２０質量部がさらに好ましい。 In the present invention, the amount of the heat-curable organic binder A added makes it easy to improve the binding force of the latent heat storage material obtained in the step (2), easily improves the hardness and solvent resistance, and makes it difficult for the microcapsules to be broken. At the same time, from the viewpoint of easily improving the latent heat amount, improving the adsorption performance, improving the dispersibility during mixing and suppressing the unevenness of the material, 5 to 30 parts by mass is preferable with respect to 100 parts by mass of the microcapsules. 8 to 25 parts by mass is more preferable, and 10 to 20 parts by mass is further preferable.
　本発明において、マイクロカプセルと熱硬化性有機バインダーＡとを混合する方法は特に制限されない。例えば、溶媒中でマイクロカプセル及び熱硬化性有機バインダーＡを常法で混合してスラリーとすることが挙げられる。 In the present invention, the method of mixing the microcapsules and the thermosetting organic binder A is not particularly limited. For example, microcapsules and a thermosetting organic binder A may be mixed in a solvent in a conventional manner to form a slurry.
　この際使用できる溶媒としては、特に制限はなく、一般的なものが使用でき、例えば、水、アルコール（メタノール、エタノール等）、これらの混合液等が挙げられる。なお、熱硬化性有機バインダーＡが、溶液、分散液、懸濁液等の形状の場合は、溶媒を使用しないこともできる。 The solvent that can be used at this time is not particularly limited, and general solvents can be used, and examples thereof include water, alcohol (methanol, ethanol, etc.), and a mixed solution thereof. When the thermosetting organic binder A is in the form of a solution, a dispersion, a suspension, or the like, a solvent may not be used.
　溶媒の添加量は、成型後のひび割れや粉化を抑制しやすく、マイクロカプセルの充填密度を高くしやすい観点から、マイクロカプセル１００質量部に対して、３～５０質量部が好ましく、５～３０質量部がより好ましく、１０～２０質量部がさらに好ましい。なお、熱硬化性有機バインダーＡが、溶液、分散液、懸濁液等の形状の場合は、当該熱硬化性有機バインダーＡ中に存在する溶媒も含めた合計量を上記範囲とすることができる。 The amount of the solvent added is preferably 3 to 50 parts by mass with respect to 100 parts by mass of the microcapsules from the viewpoint of easily suppressing cracks and powdering after molding and increasing the packing density of the microcapsules. By mass is more preferred, and 10 to 20 parts by mass is even more preferred. When the thermosetting organic binder A is in the form of a solution, a dispersion, a suspension, or the like, the total amount including the solvent present in the thermosetting organic binder A can be within the above range. ..
　この後、押出造粒は特に制限はなく、常法で行うことができ、攪拌造粒機、圧縮造粒機、押出し造粒機、転動造粒機等の一般的な造粒機を用い成型することができる。その後、必要に応じて、スクリーンダイス、ディスクダイス、ドーム型ダイス等のダイスを使用して、所望の大きさの潜熱蓄熱材となるように細粒化し、さらに、パン型造粒機、ドラムミキサー、マルメライザー等を使用して５０～１０００ｒｐｍ程度で転動させて整粒することができる。 After that, the extrusion granulation is not particularly limited and can be performed by a conventional method, and a general granulation machine such as a stirring granulation machine, a compression granulation machine, an extrusion granulation machine, or a rolling granulation machine is used. Can be molded. Then, if necessary, a die such as a screen die, a disk die, or a dome-shaped die is used to granulate the latent heat storage material to a desired size, and further, a pan-type granulator or a drum mixer. , It can be sized by rolling at about 50 to 1000 rpm using a mulmerizer or the like.
　（２－２）工程（２）
　工程（２）は、工程（１）で得られたマイクロカプセル組成物を熱硬化性有機バインダーＡで被覆し、熱処理して潜熱蓄熱材を得る工程である。 (2-2) Step (2)
The step (2) is a step of coating the microcapsule composition obtained in the step (1) with a thermosetting organic binder A and heat-treating the microcapsule composition to obtain a latent heat storage material.
　この際使用する熱硬化性有機バインダーＡは、工程（１）で使用した熱硬化性有機バインダーＡと同じものを使用してもよいし、異なるものを使用してもよい。 The thermosetting organic binder A used at this time may be the same as the thermosetting organic binder A used in the step (1), or may be different.
　上記したように、ここでは、熱硬化性有機バインダーＡが硬化した後の潜熱蓄熱材が、耐溶剤性（耐水性、耐有機溶剤性等）が高くなる熱硬化性有機バインダーＡを使用することが好ましい。例えば、耐水性については、硬化後の潜熱蓄熱材を５０℃の水に２４時間浸漬しても水が濁らないものが好ましく、さらに７０℃の水に２４時間浸漬してもが濁らないものがより好ましい。また、耐有機溶剤性については、硬化後の潜熱蓄熱材を３０℃の有機溶剤（例えば、ヘキサン、ガソリン等）に２４時間浸漬後、有機溶剤中への相変化物質の染み出し量が、潜熱蓄熱材中の相変化物質の全量に対し１５質量％以下のものが好ましく、１０質量％以下のものがより好ましい。特に、フェノール樹脂、アクリル樹脂、メラミン樹脂、アミドエステル樹脂等の耐水性を有する熱硬化性樹脂バインダーが好ましい。 As described above, here, the latent heat storage material after the thermosetting organic binder A is cured uses the thermosetting organic binder A having high solvent resistance (water resistance, organic solvent resistance, etc.). Is preferable. For example, with regard to water resistance, it is preferable that the cured latent heat storage material does not become turbid even when immersed in water at 50 ° C. for 24 hours, and further, it does not become turbid even when immersed in water at 70 ° C. for 24 hours. More preferred. Regarding the organic solvent resistance, after the cured latent heat storage material is immersed in an organic solvent at 30 ° C. (for example, hexane, gasoline, etc.) for 24 hours, the amount of the phase change substance exuded into the organic solvent is the latent heat. It is preferably 15% by mass or less, and more preferably 10% by mass or less, based on the total amount of the phase changing substance in the heat storage material. In particular, a thermosetting resin binder having water resistance such as a phenol resin, an acrylic resin, a melamine resin, and an amide ester resin is preferable.
　工程（１）で得られたマイクロカプセル組成物を被覆する熱硬化性有機バインダーＡの添加量は、活性炭の吸着熱による温度上昇を抑制しやすく、潜熱量を向上させやすく吸着性能を向上させやすいとともに耐久性も向上させやすい観点から、工程（１）で得られたマイクロカプセル組成物の総量を１００質量部として、０．５～１０質量部が好ましく、１～５質量部がより好ましく、１．５～３質量部がさらに好ましい。 The amount of the heat-curable organic binder A added to coat the microcapsule composition obtained in the step (1) is likely to suppress a temperature rise due to the heat of adsorption of the activated charcoal, easily improve the amount of latent heat, and easily improve the adsorption performance. From the viewpoint of easily improving the durability as well, the total amount of the microcapsule composition obtained in the step (1) is 100 parts by mass, preferably 0.5 to 10 parts by mass, and more preferably 1 to 5 parts by mass. .5 to 3 parts by mass is more preferable.
　工程（１）で得られたマイクロカプセル組成物を熱硬化性有機バインダーＡで被覆する方法は特に制限されない。例えば、溶媒中で一流体ノズル、二流体ノズル等を用いて被覆することができる。 The method of coating the microcapsule composition obtained in the step (1) with the thermosetting organic binder A is not particularly limited. For example, it can be coated in a solvent using a one-fluid nozzle, a two-fluid nozzle, or the like.
　この際使用できる溶媒としては、特に制限はなく、一般的なものが使用でき、例えば、水、アルコール（メタノール、エタノール等）、これらの混合液等が挙げられる。なお、熱硬化性有機バインダーＡが、溶液、分散液、懸濁液等の形状の場合は、溶媒を使用しないこともできる。 The solvent that can be used at this time is not particularly limited, and general solvents can be used, and examples thereof include water, alcohol (methanol, ethanol, etc.), and a mixed solution thereof. When the thermosetting organic binder A is in the form of a solution, a dispersion, a suspension, or the like, a solvent may not be used.
　溶媒の添加量は、成型後のひび割れや粉化を抑制しやすく、活性炭の吸着熱による温度上昇を抑制しやすく、潜熱量を向上させやすく吸着性能を向上させやすいとともに耐久性も向上させやすい観点から、工程（１）で得られたマイクロカプセル組成物の総量を１００質量部として、０．５～１０質量部が好ましく、１～５質量部がより好ましく、１．５～３質量部がさらに好ましい。なお、熱硬化性有機バインダーＡが、溶液、分散液、懸濁液等の形状の場合は、当該熱硬化性有機バインダーＡ中に存在する溶媒も含めた合計量を上記範囲とすることができる。 The amount of the solvent added is from the viewpoint that it is easy to suppress cracking and pulverization after molding, it is easy to suppress the temperature rise due to the adsorption heat of activated carbon, it is easy to improve the latent heat amount, it is easy to improve the adsorption performance, and it is easy to improve the durability. Therefore, the total amount of the microcapsule composition obtained in the step (1) is 100 parts by mass, preferably 0.5 to 10 parts by mass, more preferably 1 to 5 parts by mass, and further 1.5 to 3 parts by mass. preferable. When the thermosetting organic binder A is in the form of a solution, a dispersion, a suspension, or the like, the total amount including the solvent present in the thermosetting organic binder A can be within the above range. ..
　熱処理の際の加熱温度は特に制限はなく、活性炭の吸着熱による温度上昇を抑制しやすく、潜熱量を向上させやすく吸着性能を向上させやすいとともに耐久性も向上させやすい観点から、１００～３００℃が好ましく、１５０～２５０℃がより好ましい。 The heating temperature during the heat treatment is not particularly limited, and is 100 to 300 ° C. from the viewpoint that it is easy to suppress the temperature rise due to the adsorption heat of the activated carbon, it is easy to improve the latent heat amount, it is easy to improve the adsorption performance, and it is easy to improve the durability. Is preferable, and 150 to 250 ° C. is more preferable.
　熱処理の際の加熱時間は特に制限はなく、硬化反応を終了させて耐久性を向上させやすいため、３０～１８０分が好ましく、６０～１５０分がより好ましい。 The heating time during the heat treatment is not particularly limited, and it is easy to complete the curing reaction and improve the durability. Therefore, 30 to 180 minutes is preferable, and 60 to 150 minutes is more preferable.
　以上の熱処理により、熱硬化性有機バインダーＡを硬化させ、潜熱蓄熱材を得ることができる。 By the above heat treatment, the thermosetting organic binder A can be cured to obtain a latent heat storage material.
　（２－３）工程（３）
　工程（３）は、工程（２）で得られた潜熱蓄熱材と、活性炭を含む組成物とを混合して造粒する工程である。これにより、工程（２）で得られた潜熱蓄熱材を活性炭含有層で被覆し、本発明の潜熱蓄熱材一体型活性炭を製造することができる。 (2-3) Step (3)
The step (3) is a step of mixing and granulating the latent heat storage material obtained in the step (2) and the composition containing activated carbon. Thereby, the latent heat storage material obtained in the step (2) can be coated with the activated carbon-containing layer to produce the latent heat storage material integrated activated carbon of the present invention.
　活性炭を含む組成物は、上記した活性炭含有層を形成できるものであり、活性炭の他、必要に応じて上記有機バインダーＢ及びｐＨ調整剤を含有することができる。 The composition containing activated carbon can form the above-mentioned activated carbon-containing layer, and can contain the above-mentioned organic binder B and pH adjuster, if necessary, in addition to the activated carbon.
　活性炭を含む組成物において、有機バインダーＢの含有量は、活性炭の吸着熱による温度上昇を抑制しやすく、潜熱量を向上させやすく吸着性能を向上させやすいとともに耐久性も向上させやすい観点から、活性炭１００質量部に対して、０．５～２０質量部が好ましく、６～１１質量部がより好ましい。 In the composition containing activated carbon, the content of the organic binder B is such that the temperature rise due to the heat of adsorption of the activated carbon can be easily suppressed, the amount of latent heat can be easily improved, the adsorption performance can be easily improved, and the durability can be easily improved. With respect to 100 parts by mass, 0.5 to 20 parts by mass is preferable, and 6 to 11 parts by mass is more preferable.
　活性炭を含む組成物において、ｐＨ調整剤の含有量は、活性炭表面のバインダーの均一性を向上させやすく、硬さを向上させやすい観点から、活性炭１００質量部に対して０～１０質量部が好ましく、０～５質量部がより好ましい。 In the composition containing activated carbon, the content of the pH adjuster is preferably 0 to 10 parts by mass with respect to 100 parts by mass of activated carbon from the viewpoint of easily improving the uniformity of the binder on the surface of the activated carbon and easily improving the hardness. , 0-5 parts by mass is more preferable.
　アルカリ賦活、塩化亜鉛賦活、リン酸賦活等の薬品賦活により得られた活性炭を使用する場合は混合前にあらかじめ洗浄又は中和して、活性炭中に含まれている薬品を除去しておくことが好ましい。洗浄の方法は一般的な薬品賦活炭の洗浄方法で良く、例えば、リン酸賦活炭の場合、温水又は冷水で洗浄し、乾燥させることができる。温水又は冷水の変わりに炭酸アンモニウム水溶液のような塩基性の水溶液を使用しても良い。 When using activated carbon obtained by chemical activation such as alkali activation, zinc chloride activation, phosphoric acid activation, etc., it is necessary to wash or neutralize the activated carbon in advance before mixing to remove the chemicals contained in the activated carbon. preferable. The washing method may be a general washing method of chemical-activated charcoal. For example, in the case of phosphoric acid-activated charcoal, it can be washed with hot water or cold water and dried. A basic aqueous solution such as an ammonium carbonate aqueous solution may be used instead of hot water or cold water.
　活性炭を含む組成物には、成型後のひび割れや粉化を抑制しやすい観点から、溶媒を含んでいてもよい。 The composition containing activated carbon may contain a solvent from the viewpoint of easily suppressing cracking and pulverization after molding.
　この際使用できる溶媒としては、特に制限はなく、一般的なものが使用でき、例えば、水、アルコール（メタノール、エタノール等）、これらの混合液等が挙げられる。なお、有機バインダーＢが、溶液、分散液、懸濁液等の形状の場合は、溶媒を使用しないこともできる。 The solvent that can be used at this time is not particularly limited, and general solvents can be used, and examples thereof include water, alcohol (methanol, ethanol, etc.), and a mixed solution thereof. When the organic binder B is in the form of a solution, a dispersion, a suspension, or the like, a solvent may not be used.
　溶媒の添加量は、成型後のひび割れや粉化を抑制しやすく、活性炭の吸着熱による温度上昇を抑制しやすく、潜熱量を向上させやすく吸着性能を向上させやすいとともに耐久性も向上させやすい観点から、活性炭１００質量部に対して、５０～１５００質量部が好ましく、１００～５００質量部がより好ましく、３００～６５０質量部がさらに好ましい。なお、有機バインダーＢが、溶液、分散液、懸濁液等の形状の場合は、当該有機バインダーＢ中に存在する溶媒も含めた合計量を上記範囲とすることができる。 The amount of the solvent added is easy to suppress cracking and pulverization after molding, easy to suppress the temperature rise due to the adsorption heat of activated carbon, easy to improve the latent heat amount, easy to improve the adsorption performance, and easy to improve the durability. Therefore, 50 to 1500 parts by mass is preferable, 100 to 500 parts by mass is more preferable, and 300 to 650 parts by mass is further preferable with respect to 100 parts by mass of activated carbon. When the organic binder B is in the form of a solution, a dispersion, a suspension, or the like, the total amount including the solvent present in the organic binder B can be in the above range.
　この後、工程（２）で得られた潜熱蓄熱材と、活性炭を含む組成物とを混合して造粒する（工程（２）で得られた潜熱蓄熱材を活性炭含有層で被覆する）方法は特に制限されず、従来から公知の造粒法を採用することができる。例えば、工程（２）で得られた潜熱蓄熱材及び活性炭を含む組成物に結合剤を加えて練合し、練合物をスクリーンから押出して成形造粒する方法である押出し造粒法；上記の方法で練合して調製した練合塊を造粒機の回転刃で切断し、遠心力により外周のスクリューの目からはじき出す方法である解砕造粒法；工程（２）で得られた潜熱蓄熱材及び活性炭を含む組成物に結合剤を加えて加湿した粉体に回転運動又は振動を与えて凝集させ、球状に近い粒子を得る方法である転動造粒法；工程（２）で得られた潜熱蓄熱材及び活性炭を含む組成物を下方から熱気流により流動させ、これに結合剤を噴霧して造粒する方法である流動層造粒法；工程（２）で得られた潜熱蓄熱材及び活性炭を含む組成物を容器に投入して回転するブレードで撹拌しながら水又は造粒液体を添加して、原料粉粒体を球形に凝集させる撹拌造粒法等を制限なく例示することができる。この際、マルメライザー、噴霧造粒、流動層造粒、攪拌造粒機、パン型造粒機等を用いて成型することができる。 After that, the latent heat storage material obtained in the step (2) and the composition containing activated carbon are mixed and granulated (the latent heat storage material obtained in the step (2) is coated with the activated carbon-containing layer). Is not particularly limited, and a conventionally known granulation method can be adopted. For example, the extrusion granulation method is a method in which a binder is added to a composition containing a latent heat storage material and activated charcoal obtained in step (2) and kneaded, and the kneaded product is extruded from a screen to form and granulate. The crushing and granulating method, which is a method in which the kneaded mass prepared by kneading in the above method is cut with a rotary blade of a granulator and ejected from the outer screw eyes by centrifugal force; obtained in step (2). Rolling granulation method, which is a method of obtaining particles close to spheres by applying a rotating motion or vibration to a humidified powder by adding a binder to a composition containing a latent heat storage material and activated charcoal to agglomerate the powder. The fluidized layer granulation method is a method in which the obtained composition containing the latent heat storage material and the activated charcoal is flowed from below by a hot air stream, and a binder is sprayed onto the composition to granulate the composition; the latent heat obtained in the step (2). An unlimited example of a stirring granulation method in which a composition containing a heat storage material and activated charcoal is put into a container and water or a granulating liquid is added while stirring with a rotating blade to agglomerate raw material powders and granules into a spherical shape. be able to. At this time, it can be molded by using a mulmerizer, spray granulation, fluidized bed granulation, stirring granulation machine, bread type granulation machine and the like.
　使用する活性炭を含む組成物の添加量は、特に制限はなく、成型後のひび割れや粉化を抑制しやすく、活性炭の吸着熱による温度上昇を抑制しやすく、潜熱量を向上させやすく吸着性能を向上させやすいとともに耐久性も向上させやすい観点から、工程（２）で得られた潜熱蓄熱材１００質量部に対して、２００～１０００質量部が好ましく、２５０～６００質量部がより好ましい。 The amount of the composition containing activated carbon to be used is not particularly limited, and it is easy to suppress cracking and pulverization after molding, it is easy to suppress the temperature rise due to the heat of adsorption of activated carbon, and it is easy to improve the amount of latent heat to improve the adsorption performance. From the viewpoint of easy improvement and easy improvement of durability, 200 to 1000 parts by mass is preferable, and 250 to 600 parts by mass is more preferable with respect to 100 parts by mass of the latent heat storage material obtained in the step (2).
　この際、結合剤としては、特に制限されず、例えば、メチルセルロース、エチルセルロース、ヒドロキシエチルセルロース、ヒドロキシプロピルセルロース、ヒプロメロース、カルボキシメチルセルロース等のセルロース誘導体；結晶セルロース、ポリビニルアルコール、ポリビニルピロリドン（ポビドン）、ビニルピロリドン共重合体（コポリビドン）、アクリル酸系高分子、ゼラチン、アラビアゴム、プルラン、カンテン、トラガント、アルギン酸ナトリウム、アルギン酸プロピレングリコールエステル、α化デンプン、デキストリン、マクロゴール、白糖等が挙げられる。これらの結合剤を、水溶液等の溶液状として使用することもできる。これらの結合剤は、単独で用いることもでき、２種以上を組合せて用いることもできる。 At this time, the binder is not particularly limited, and for example, cellulose derivatives such as methyl cellulose, ethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, hypromellose, and carboxymethyl cellulose; crystalline cellulose, polyvinyl alcohol, polyvinylpyrrolidone (povidone), and vinylpyrrolidone are used. Examples thereof include polymers (copolyvidone), acrylic acid-based polymers, gelatin, gum arabic, purulan, canten, tragant, sodium alginate, propylene glycol alginate, pregelatinized starch, dextrin, macrogol, and sucrose. These binders can also be used in the form of a solution such as an aqueous solution. These binders can be used alone or in combination of two or more.
　以上の結合剤の使用量は、成型後のひび割れや粉化を抑制しやすい観点から、工程（２）で得られた潜熱蓄熱材１００質量部に対して、固形分で１５～１００質量部が好ましく、１７～８５質量部がより好ましい。 The amount of the above binder used is 15 to 100 parts by mass in terms of solid content with respect to 100 parts by mass of the latent heat storage material obtained in step (2) from the viewpoint of easily suppressing cracks and powdering after molding. Preferably, 17 to 85 parts by mass is more preferable.
　この後、本発明の潜熱蓄熱材一体型活性炭を成型しやすくするため、熱処理することが好ましい。 After that, it is preferable to heat-treat the activated carbon integrated with the latent heat storage material of the present invention in order to facilitate molding.
　熱処理の際の加熱温度は特に制限はなく、活性炭の吸着熱による温度上昇を抑制しやすく、潜熱量を向上させやすく吸着性能を向上させやすいとともに耐久性も向上させやすい観点から、８０～２５０℃が好ましく、１００～２００℃がより好ましい。 The heating temperature during the heat treatment is not particularly limited, and is 80 to 250 ° C. from the viewpoint that it is easy to suppress the temperature rise due to the adsorption heat of the activated carbon, it is easy to improve the latent heat amount, it is easy to improve the adsorption performance, and it is easy to improve the durability. Is preferable, and 100 to 200 ° C. is more preferable.
　熱処理の際の加熱時間は特に制限はなく、十分に小粒径且つ真球度の高い球状活性炭を得られる時間とすることができ、活性炭の吸着熱による温度上昇を抑制しやすく、潜熱量を向上させやすく吸着性能を向上させやすいとともに耐久性も向上させやすい観点から、１０分～１２時間が好ましく、３０分～６時間がより好ましい。この際、得られる本発明の潜熱蓄熱材一体型活性炭の含水率が１０質量％以下、特に５質量％以下となるように調整することが好ましい。 The heating time during the heat treatment is not particularly limited, and can be set to a time during which a spherical activated carbon having a sufficiently small particle size and high sphericity can be obtained. From the viewpoint of easy improvement, easy improvement of adsorption performance and easy improvement of durability, 10 minutes to 12 hours is preferable, and 30 minutes to 6 hours is more preferable. At this time, it is preferable to adjust the water content of the obtained latent heat storage material-integrated activated carbon of the present invention to be 10% by mass or less, particularly 5% by mass or less.
　以下に実施例及び比較例を示して本発明を具体的に説明する。但し、本発明は実施例の態様に限定されない。 Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples. However, the present invention is not limited to the embodiments of the examples.
　なお、以下の実施例及び比較例において、マイクロカプセルの平均粒子径はレーザー回折式粒子径分布測定装置（マイクロトラック・ベル（株）製：マイクロトラックＭＴ３３００ＥＸＩＩ）により測定し、潜熱蓄熱材の平均断面直径はノギスでペレット１０本分を測定し、潜熱蓄熱材の熱量はＤＳＣ７０２０（示差走査熱量計、セイコーインスツル（株）製）により測定した。 In the following Examples and Comparative Examples, the average particle size of the microcapsules was measured by a laser diffraction type particle size distribution measuring device (Microtrack Bell Co., Ltd .: Microtrack MT3300EXII), and the average cross section of the latent heat storage material was measured. The diameter was measured for 10 pellets with a caliper, and the calorific value of the latent heat storage material was measured with a DSC7020 (differential scanning calorimeter, manufactured by Seiko Instruments Co., Ltd.).
　なお、以下の実施例及び比較例において、マイクロカプセルを調製する方法において、「既存の方法」とは、ホルマリン縮合型樹脂の初期縮合物を使用したインサイチュ（ｉｎ－ｓｉｔｕ）法を採用し、以下の操作によってマイクロカプセルを調製したことを意味する：ｐＨを４．５に調整したスチレン無水マレイン酸共重合体のナトリウム塩水溶液をホモミキサーで激しく撹拌しながら、相変化物質として上記乳化剤の２倍のモル数となるよう、相転移温度が所定の温度である所定の相転移物質を徐々に添加して平均粒子径が３．０～４．０μｍになるまで乳化した。一方、メラミン：ホルムアルデヒド：水がモル数で１：２：７となるように混合しｐＨ１０に調整し攪拌しながら６０℃に加熱して初期縮合物を得た。上記の乳化液を別容器に写し、メラミンホルマリン初期縮合物を添加し、８０℃で３時間反応させて、マイクロカプセルに対してメラミン膜の割合率が１７％となるマイクロカプセルの水分散液（固形分４０重量％）を得てｐＨを９に調整しカプセル化を行った。当該マイクロカプセルの水分散液に対して０．５質量％となるようにポリビニルアルコールを加え、再度攪拌を行った後、スプレードライ法にて乾燥することによってマイクロカプセルを得た。 In the following Examples and Comparative Examples, in the method for preparing microcapsules, the "existing method" is an in-situ method using an initial condensate of a formalin condensation type resin. It means that the microcapsules were prepared by the above operation: The sodium salt aqueous solution of the styrene anhydride maleic acid copolymer whose pH was adjusted to 4.5 was vigorously stirred with a homomixer, and the phase change substance was twice that of the above emulsion. A predetermined phase transition substance having a predetermined phase transition temperature was gradually added so as to have the number of moles of the above, and emulsification was performed until the average particle size became 3.0 to 4.0 μm. On the other hand, melamine: formaldehyde: water was mixed so as to have a molar number of 1: 2: 7, adjusted to pH 10, and heated to 60 ° C. with stirring to obtain an initial condensate. The above emulsion is transferred to a separate container, the melamine formalin initial condensate is added, and the mixture is reacted at 80 ° C. for 3 hours to obtain a microcapsule aqueous dispersion in which the ratio of the melamine film to the microcapsules is 17%. Solid content (40% by weight) was obtained, the pH was adjusted to 9, and encapsulation was performed. Polyvinyl alcohol was added so as to be 0.5% by mass with respect to the aqueous dispersion of the microcapsules, the mixture was stirred again, and then dried by a spray-drying method to obtain microcapsules.
　なお、活性炭又は潜熱蓄熱材一体型活性炭のｐＨについては、ＪＩＳ　Ｋ　１４７４（２０１４）に準拠して、活性炭は１．０ｇ、潜熱蓄熱材一体型活性炭や製造例及び比較製造例の成型物は３．０ｇを１００ｍＬの水に添加し、沸騰が続くように５分間加熱した後に室温まで冷却し、水を添加して１００ｍＬとして得た水懸濁液のｐＨを、ｐＨ計を用いて測定した。 Regarding the pH of the activated carbon or the latent heat storage material integrated activated carbon, according to JIS K 1474 (2014), the activated carbon weighs 1.0 g, and the latent heat storage material integrated activated carbon and the molded products of the production example and the comparative production example are 3 0.0 g was added to 100 mL of water, heated for 5 minutes so that boiling continued, cooled to room temperature, and the pH of the aqueous suspension obtained by adding water to 100 mL was measured using a pH meter.
　実施例１
　相転移温度が５０～５２℃を有する直鎖の脂肪族炭化水素を内包物とし既存の方法で作製した、メラミン膜で覆ったマイクロカプセルを使用した。 Example 1
Microcapsules covered with a melamine membrane prepared by an existing method containing a linear aliphatic hydrocarbon having a phase transition temperature of 50 to 52 ° C. were used.
　上記したマイクロカプセル１００質量部に対して、１７質量部の熱硬化性フェノール系有機バインダー（ＤＩＣ（株）製のフェノライト１４８０；固形分６８.７質量％）、及び１８質量部の水を添加して混合した。その後、混合物を、押出し機（（株）ダルトン製のディスクペレッターＦ５型）で成型した。このとき、スクリーンダイスの目開きは１．０ｍｍを用いて細粒化した。その後、マルメライザー（（株）ダルトン製のＱＪ－４００型）を用いて、２７５ｒｐｍで２分整粒し、マイクロカプセル組成物を得た。 To 100 parts by mass of the above microcapsules, 17 parts by mass of a thermosetting phenol-based organic binder (phenolite 1480 manufactured by DIC Corporation; solid content 68.7% by mass) and 18 parts by mass of water were added. And mixed. Then, the mixture was molded by an extruder (disc pelleter F5 type manufactured by Dalton Co., Ltd.). At this time, the opening of the screen die was finely divided using 1.0 mm. Then, using Malmerizer (QJ-400 type manufactured by Dalton Co., Ltd.), the granules were sized for 2 minutes at 275 rpm to obtain a microcapsule composition.
　次に、得られたマイクロカプセル組成物を用いて、上記と同様の熱硬化型フェノール系バインダーでコーティングした。具体的には、得られたマイクロカプセル組成物１００質量部に対して、上記熱硬化型フェノール系バインダーを１．５質量部、溶媒として水をバインダーと等量部添加し、１流体ノズルを用いてマイクロカプセルに熱硬化型フェノール系バインダーを被覆し、材温が１６０℃以上となるように設定し、２時間乾燥させ、潜熱蓄熱材を得た。 Next, the obtained microcapsule composition was used and coated with a thermosetting phenolic binder similar to the above. Specifically, 1.5 parts by mass of the heat-curable phenolic binder and an equal amount of water as a solvent were added to 100 parts by mass of the obtained microcapsule composition, and a one-fluid nozzle was used. The microcapsules were coated with a heat-curable phenolic solvent, the material temperature was set to 160 ° C. or higher, and the cells were dried for 2 hours to obtain a latent heat storage material.
　あらかじめ、活性炭と有機バインダーと水とを混練し、解砕することで混合物（活性炭を含む組成物）を得た。この際、有機バインダーとしては、カルボキシメチルセルロースナトリウム塩（日本製紙（株）製のＦ３０ＭＣ）、エポクロスＷＳ－７００（（株）日本触媒製のオキサゾリン基含有水溶性ポリマー）、ＡＤＥＫＡレジン（（株）ＡＤＥＫＡ製の水性エポキシ樹脂ＥＭ－０１８０）を選定し、固形分率で活性炭１００質量部に対してそれぞれ７．２質量部、１．２質量部、２．１質量部の計１０．５質量部、水は活性炭１００質量部に対して１６０．５質量部を加えた。 The activated carbon, the organic binder and water were kneaded in advance and crushed to obtain a mixture (composition containing activated carbon). At this time, as the organic binder, carboxymethyl cellulose sodium salt (F30MC manufactured by Nippon Paper Co., Ltd.), Epocross WS-700 (oxazoline group-containing water-soluble polymer manufactured by Nippon Catalyst Co., Ltd.), ADEKA Resin (ADEKA Corporation) Made of water-based epoxy resin EM-0180) was selected, and the solid content was 7.2 parts by mass, 1.2 parts by mass, and 2.1 parts by mass, for a total of 10.5 parts by mass with respect to 100 parts by mass of activated carbon. 160.5 parts by mass of water was added to 100 parts by mass of activated charcoal.
　次に、得られた実施例１の潜熱蓄熱材を核として、造粒機（自社製）に２５０ｇを投入し、０．０１質量％ＰＶＡ溶液水を１．５～２．０Ｌ噴霧しながら、流動させつつ、上記した混合物（活性炭を含む組成物）を１５４０ｇ分が全量使用されるようにコーティング（厚み７３０μｍ）に供した（潜熱蓄熱材：活性炭：有機バインダー＝２５０：１３９５：１４６（質量比）である）。その後、１１５℃で３時間以上乾燥させ、成型物の含水率を５質量％未満とし、平均粒子径を２．４～２．８ｍｍに調整し、実施例１の潜熱蓄熱材一体型活性炭を得た。 Next, using the obtained latent heat storage material of Example 1 as a core, 250 g was put into a granulator (manufactured in-house), and while spraying 1.5 to 2.0 L of 0.01 mass% PVA solution water, While flowing, the above mixture (composition containing activated charcoal) was applied to a coating (thickness 730 μm) so that the entire amount of 1540 g was used (latent heat storage material: activated charcoal: organic binder = 250: 1395: 146 (mass ratio). ). Then, it was dried at 115 ° C. for 3 hours or more, the water content of the molded product was set to less than 5% by mass, the average particle size was adjusted to 2.4 to 2.8 mm, and the latent heat storage material integrated activated carbon of Example 1 was obtained. rice field.
　実施例２
　相転移温度が４５～４７℃を有する直鎖の脂肪族炭化水素を内包物とし既存の方法で作製した、メラミン膜で覆ったマイクロカプセルを使用した他は実施例１と同様に、潜熱蓄熱材を得た。その後、実施例１と同様にして、実施例２の潜熱蓄熱材一体型活性炭を得た。 Example 2
A latent heat storage material as in Example 1, except that microcapsules covered with a melamine film prepared by an existing method using a linear aliphatic hydrocarbon having a phase transition temperature of 45 to 47 ° C. were used. Got Then, in the same manner as in Example 1, the latent heat storage material integrated activated carbon of Example 2 was obtained.
　実施例３
　相転移温度が４２～４５℃を有する直鎖の脂肪族炭化水素（炭素数２２）を内包物とし既存の方法で作製した、メラミン膜で覆ったマイクロカプセルを使用しスクリーンダイスの目開きは０．８ｍｍを用いて細粒化した他は実施例１と同様に、潜熱蓄熱材を得た。その後、活性炭を含む組成物を１９２４ｇ分が全量使用されるようにコーティング（厚み６６０μｍ）に供した（潜熱蓄熱材：活性炭：有機バインダー＝２５０：１７４２：１８２（質量比）である）。その後、１１５℃で３時間以上乾燥させ、成型物の含水率を５質量％未満とし、平均粒子径を２．０～２．４ｍｍに調製した他は実施例１と同様にして、実施例３の潜熱蓄熱材一体型活性炭を得た。 Example 3
Using microcapsules covered with a melamine film prepared by an existing method using a linear aliphatic hydrocarbon (22 carbon atoms) having a phase transition temperature of 42 to 45 ° C., the opening of the screen die is 0. A latent heat storage material was obtained in the same manner as in Example 1 except that the particles were finely divided using 0.8 mm. Then, the composition containing activated carbon was applied to a coating (thickness: 660 μm) so that the entire amount of 1924 g was used (latent heat storage material: activated carbon: organic binder = 250: 1742: 182 (mass ratio)). Then, it was dried at 115 ° C. for 3 hours or more, the water content of the molded product was set to less than 5% by mass, and the average particle size was adjusted to 2.0 to 2.4 mm. The activated carbon integrated with the latent heat storage material was obtained.
　実施例４
　相転移温度が４２～４５℃を有する直鎖の脂肪族炭化水素（炭素数２２）を内包物とし既存の方法で作製した、メラミン膜で覆ったマイクロカプセルを使用した他は実施例１と同様に、潜熱蓄熱材を得た。その後、実施例１と同様にして、実施例４の潜熱蓄熱材一体型活性炭を得た。 Example 4
Same as in Example 1 except that microcapsules covered with a melamine film prepared by an existing method using a linear aliphatic hydrocarbon (carbon number 22) having a phase transition temperature of 42 to 45 ° C. were used as inclusions. In addition, a latent heat storage material was obtained. Then, in the same manner as in Example 1, the latent heat storage material integrated activated carbon of Example 4 was obtained.
　実施例５
　相転移温度が４２～４５℃を有する直鎖の脂肪族炭化水素（炭素数２２）を内包物とし既存の方法で作製した、メラミン膜で覆ったマイクロカプセルを使用しスクリーンダイスの目開きは１．２ｍｍを用いて細粒化した他は実施例１と同様に、潜熱蓄熱材を得た。その後、活性炭を含む組成物を６４０ｇ分が全量使用されるようにコーティング（厚み５３５μｍ）に供した（潜熱蓄熱材：活性炭：有機バインダー＝２５０：５７９：６１（質量比）である）。その後、１１５℃で３時間以上乾燥させ、成型物の含水率を５質量％未満とし、平均粒子径を２．０～２．４ｍｍに調製した他は実施例１と同様にして、実施例５の潜熱蓄熱材一体型活性炭を得た。 Example 5
Using microcapsules covered with a melamine film prepared by an existing method using a linear aliphatic hydrocarbon (22 carbon atoms) having a phase transition temperature of 42 to 45 ° C., the opening of the screen die is 1. A latent heat storage material was obtained in the same manner as in Example 1 except that the particles were finely divided using 2 mm. Then, the composition containing activated carbon was applied to a coating (thickness: 535 μm) so that the entire amount of 640 g was used (latent heat storage material: activated carbon: organic binder = 250: 579: 61 (mass ratio)). Then, it was dried at 115 ° C. for 3 hours or more, the water content of the molded product was set to less than 5% by mass, and the average particle size was adjusted to 2.0 to 2.4 mm. The activated carbon integrated with the latent heat storage material was obtained.
　実施例６
　相転移温度が３２～３７℃を有する直鎖の脂肪族炭化水素（炭素数２０）を内包物とし既存の方法で作製した、メラミン膜で覆ったマイクロカプセルを使用した他は実施例１と同様に、潜熱蓄熱材を得た。その後、実施例１と同様にして、実施例６の潜熱蓄熱材一体型活性炭を得た。 Example 6
Same as in Example 1 except that microcapsules covered with a melamine film prepared by an existing method using a linear aliphatic hydrocarbon (carbon number 20) having a phase transition temperature of 32 to 37 ° C. were used as inclusions. In addition, a latent heat storage material was obtained. Then, in the same manner as in Example 1, the latent heat storage material integrated activated carbon of Example 6 was obtained.
　実施例７
　相転移温度が１８℃を有する直鎖の脂肪族炭化水素（炭素数１６）を内包物とし既存の方法で作製した、メラミン膜で覆ったマイクロカプセルを使用した他は実施例１と同様に、潜熱蓄熱材を得た。その後、実施例１と同様にして、実施例７の潜熱蓄熱材一体型活性炭を得た。 Example 7
Similar to Example 1, except that microcapsules covered with a melamine film prepared by an existing method using a linear aliphatic hydrocarbon (16 carbon atoms) having a phase transition temperature of 18 ° C. as an inclusion were used. A latent heat storage material was obtained. Then, in the same manner as in Example 1, the latent heat storage material integrated activated carbon of Example 7 was obtained.
　比較例１
　相転移温度が５０～５２℃を有する直鎖の脂肪族炭化水素を内包物とし既存の方法で作製した、メラミン膜で覆ったマイクロカプセルとして、実施例１で用いたマイクロカプセルを用いて、実施例１と同様にマイクロカプセル組成物を製造し、潜熱蓄熱材とした。つまり、マイクロカプセルの表面に熱硬化性有機バインダーでコーティングしなかった。その後、実施例１と同様にして、比較例１の潜熱蓄熱材一体型活性炭を得た。 Comparative Example 1
The microcapsules used in Example 1 were used as microcapsules covered with a melamine membrane prepared by an existing method using a linear aliphatic hydrocarbon having a phase transition temperature of 50 to 52 ° C. as an inclusion. A microcapsule composition was produced in the same manner as in Example 1 and used as a latent heat storage material. That is, the surface of the microcapsules was not coated with a thermosetting organic binder. Then, in the same manner as in Example 1, the latent heat storage material integrated activated carbon of Comparative Example 1 was obtained.
　比較例２
　相転移温度が４５～４７℃を有する直鎖の脂肪族炭化水素を内包物とし既存の方法で作製した、メラミン膜で覆ったマイクロカプセルを用いて、実施例１と同様にマイクロカプセル組成物を製造し、潜熱蓄熱材とした。つまり、マイクロカプセルの表面に熱硬化性有機バインダーでコーティングしなかった。その後、実施例１と同様にして、比較例２の潜熱蓄熱材一体型活性炭を得た。 Comparative Example 2
A microcapsule composition was prepared in the same manner as in Example 1 using microcapsules covered with a melamine film prepared by an existing method using a linear aliphatic hydrocarbon having a phase transition temperature of 45 to 47 ° C. as an inclusion. Manufactured and used as a latent heat storage material. That is, the surface of the microcapsules was not coated with a thermosetting organic binder. Then, in the same manner as in Example 1, the latent heat storage material integrated activated carbon of Comparative Example 2 was obtained.
　比較例３
　相転移温度が４２～４５℃を有する直鎖の脂肪族炭化水素（炭素数２２）を内包物とし既存の方法で作製した、メラミン膜で覆ったマイクロカプセルを用いて、実施例１と同様にマイクロカプセル組成物を製造し、潜熱蓄熱材とした。つまり、マイクロカプセルの表面に熱硬化性有機バインダーでコーティングしなかった。その後、実施例１と同様にして、比較例３の潜熱蓄熱材一体型活性炭を得た。 Comparative Example 3
Similar to Example 1, using microcapsules covered with a melamine film prepared by an existing method using a linear aliphatic hydrocarbon (carbon number 22) having a phase transition temperature of 42 to 45 ° C. as an inclusion. A microcapsule composition was produced and used as a latent heat storage material. That is, the surface of the microcapsules was not coated with a thermosetting organic binder. Then, in the same manner as in Example 1, the latent heat storage material integrated activated carbon of Comparative Example 3 was obtained.
　比較例４
　相転移温度が３２～３７℃を有する直鎖の脂肪族炭化水素（炭素数２０）を内包物とし既存の方法で作製した、メラミン膜で覆ったマイクロカプセルを用いて、実施例１と同様にマイクロカプセル組成物を製造し、潜熱蓄熱材とした。つまり、マイクロカプセルの表面に熱硬化性有機バインダーでコーティングしなかった。その後、実施例１と同様にして、比較例４の潜熱蓄熱材一体型活性炭を得た。 Comparative Example 4
Similar to Example 1, using microcapsules covered with a melamine film prepared by an existing method using a linear aliphatic hydrocarbon (carbon number 20) having a phase transition temperature of 32 to 37 ° C. as an inclusion. A microcapsule composition was produced and used as a latent heat storage material. That is, the surface of the microcapsules was not coated with a thermosetting organic binder. Then, in the same manner as in Example 1, the latent heat storage material integrated activated carbon of Comparative Example 4 was obtained.
　比較例５
　相転移温度が１８℃を有する直鎖の脂肪族炭化水素（炭素数１６）を内包物とし既存の方法で作製した、メラミン膜で覆ったマイクロカプセルを用いて、実施例１と同様にマイクロカプセル組成物を製造し、潜熱蓄熱材とした。つまり、マイクロカプセルの表面に熱硬化性有機バインダーでコーティングしなかった。その後、実施例１と同様にして、比較例５の潜熱蓄熱材一体型活性炭を得た。 Comparative Example 5
Using a microcapsule covered with a melamine film prepared by an existing method using a linear aliphatic hydrocarbon (16 carbon atoms) having a phase transition temperature of 18 ° C., the microcapsule is the same as in Example 1. The composition was produced and used as a latent heat storage material. That is, the surface of the microcapsules was not coated with a thermosetting organic binder. Then, in the same manner as in Example 1, the latent heat storage material integrated activated carbon of Comparative Example 5 was obtained.
　比較例６
　相転移温度が４２～４５℃を有する直鎖の脂肪族炭化水素（炭素数２２）を内包物とし既存の方法で作製した、メラミン膜で覆ったマイクロカプセルを用いて、スクリーンダイスの目開きは０．７ｍｍを用いて細粒化した他は実施例１と同様に、潜熱蓄熱材を得た。活性炭を含む組成物を４１４０ｇ分が全量使用されるようにコーティング（厚み８００μｍ）に供した（潜熱蓄熱材：活性炭：有機バインダー＝２５０：３７４８：３９２（質量比）である）。その後、１１５℃で３時間以上乾燥させ、成型物の含水率を５質量％未満とし、平均粒子径を２．０～２．４ｍｍに調製した他は実施例１と同様にして、比較例６の潜熱蓄熱材一体型活性炭を得た。 Comparative Example 6
Using microcapsules covered with a melamine film prepared by an existing method using a linear aliphatic hydrocarbon (22 carbon atoms) having a phase transition temperature of 42 to 45 ° C., the opening of the screen die is opened. A latent heat storage material was obtained in the same manner as in Example 1 except that the particles were finely divided using 0.7 mm. The composition containing activated carbon was applied to a coating (thickness 800 μm) so that the entire amount of 4140 g was used (latent heat storage material: activated carbon: organic binder = 250: 3748: 392 (mass ratio)). Then, it was dried at 115 ° C. for 3 hours or more, the water content of the molded product was set to less than 5% by mass, and the average particle size was adjusted to 2.0 to 2.4 mm. The activated carbon integrated with the latent heat storage material was obtained.
　試験例１
　ポータブルリアクター耐圧容器（耐圧硝子工業（株）製のＴＶＳ-１型）に、実施例１～７及び比較例１～６で得た潜熱蓄熱材一体型活性炭３ｇを投入し、ガソリンを１０ｍＬ投入した。その後、７０℃で４８時間加熱処理した後、該潜熱蓄熱材一体型活性炭をシャーレ上に取り出し、それらを３０ｍＬのヘキサン（富士フイルム和光純薬（株）製の試薬特級）で洗い流した後、送風低温乾燥機（ヤマト科学（株）製のＤＫ３４０Ｓ）を用いて４０℃で２時間乾燥させた。その後ＤＳＣ７０２０（示差走査熱量計、セイコーインスツル（株）製）を用いて熱量を測定した。ガソリン処理後の熱量を未処理時の熱量で割り、熱量残存率を算出した。結果を表１に示す。 Test Example 1
3 g of the latent heat storage material integrated activated carbon obtained in Examples 1 to 7 and Comparative Examples 1 to 6 was charged into a portable reactor pressure-resistant container (TVS-1 type manufactured by Pressure-Resistant Glass Industry Co., Ltd.), and 10 mL of gasoline was charged. .. Then, after heat-treating at 70 ° C. for 48 hours, the activated carbon integrated with the latent heat storage material was taken out on a petri dish, washed with 30 mL of hexane (special grade reagent manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), and then blown. It was dried at 40 ° C. for 2 hours using a low temperature dryer (DK340S manufactured by Yamato Scientific Co., Ltd.). After that, the calorific value was measured using DSC7020 (differential scanning calorimeter, manufactured by Seiko Instruments Inc.). The calorific value after gasoline treatment was divided by the calorific value at the time of untreatment to calculate the calorific value residual ratio. The results are shown in Table 1.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
　実施例１～７と比較例１～５とを比較することで、マイクロカプセルの外表面が、熱硬化性有機バインダーでコーティングされることでガソリン浸漬試験後における潜熱蓄熱材が有する熱量の残存率が９３％以上と高いことがわかり、コーティングがないと熱量の残存量が著しく低下することが分かる（５３～５６％）。これにより、マイクロカプセルに熱硬化性有機バインダーでコーティングすることの効果が高いことが分かる。さらに、相変化物質の種類によらず、同じ傾向が得られた。 By comparing Examples 1 to 7 and Comparative Examples 1 to 5, the outer surface of the microcapsules is coated with a thermosetting organic binder, so that the residual rate of the amount of heat possessed by the latent heat storage material after the gasoline immersion test Is as high as 93% or more, and it can be seen that the residual amount of heat is significantly reduced without coating (53 to 56%). From this, it can be seen that the effect of coating the microcapsules with a thermosetting organic binder is high. Furthermore, the same tendency was obtained regardless of the type of phase change substance.
　一方、比較例６のとおり潜熱蓄熱材の平均断面直径が０．７ｍｍより小さくなると、ガソリン浸漬試験による耐久試験にてガソリンのペレットへの侵入が多くなるため、耐久性能が著しく低下する結果となっている。 On the other hand, if the average cross-sectional diameter of the latent heat storage material is smaller than 0.7 mm as in Comparative Example 6, the durability performance is significantly deteriorated because the gasoline penetrates into the pellets more frequently in the durability test by the gasoline immersion test. ing.
　試験例１を実施後、熱硬化性有機バインダーでコーティングした潜熱蓄熱材一体型活性炭（実施例４）中の潜熱蓄熱材と熱硬化性有機バインダーでコーティングしない潜熱蓄熱材一体型活性炭（比較例３）中の潜熱蓄熱材のＳＥＭ画像を比較したものを図１～２に示す。なお、各潜熱蓄熱材は、ハンマーで叩くことによって各潜熱蓄熱材一体型活性炭から表面の活性炭含有層を剥離したものを評価した。熱硬化性有機バインダーでコーティングしたものはひび割れが少なく、熱硬化性有機バインダーでコーティングしないものはひび割れが多くなっており、中の内包物が溶剤で抜け出てしまい、残存熱量が低下することが分かる。 After carrying out Test Example 1, the latent heat storage material in the latent heat storage material integrated activated carbon coated with the thermosetting organic binder (Example 4) and the latent heat storage material integrated activated carbon not coated with the heat curable organic binder (Comparative Example 3). 1 and 2 show a comparison of SEM images of the latent heat storage material in). For each latent heat storage material, the one in which the activated carbon-containing layer on the surface was peeled off from each latent heat storage material integrated activated carbon by hitting with a hammer was evaluated. It can be seen that those coated with a thermosetting organic binder have less cracks, and those not coated with a thermosetting organic binder have more cracks, and the inclusions inside are removed by the solvent, reducing the amount of residual heat. ..
　実施例８
　あらかじめ、活性炭と有機バインダーと水とを混練し、解砕することで混合物（活性炭を含む組成物）を得た。この際、有機バインダーとしては、カルボキシメチルセルロースナトリウム塩（日本製紙（株）製のＦ３０ＭＣ）、エポクロスＷＳ－７００（（株）日本触媒製のオキサゾリン基含有水溶性ポリマー）、ＡＤＥＫＡレジン（（株）ＡＤＥＫＡ製の水性エポキシ樹脂ＥＭ－０１８０）を選定し、固形分率で活性炭１００質量部に対してそれぞれ７．２質量部、１．２質量部、２．１質量部の計１０．５質量部、水は活性炭１００質量部に対して１６０．５質量部を加えた。 Example 8
A mixture (composition containing activated carbon) was obtained by kneading activated carbon, an organic binder, and water in advance and crushing the mixture. At this time, as the organic binder, carboxymethyl cellulose sodium salt (F30MC manufactured by Nippon Paper Co., Ltd.), Epocross WS-700 (oxazoline group-containing water-soluble polymer manufactured by Nippon Catalyst Co., Ltd.), ADEKA Resin Co., Ltd. ADEKA Made of water-based epoxy resin EM-0180) was selected, and the solid content was 7.2 parts by mass, 1.2 parts by mass, and 2.1 parts by mass, for a total of 10.5 parts by mass with respect to 100 parts by mass of activated carbon. 160.5 parts by mass of water was added to 100 parts by mass of activated charcoal.
　次に、実施例３で得られた潜熱蓄熱材を核として、造粒機（自社製）に２５０ｇを投入し、０．０１質量％ＰＶＡ溶液水を１．５～２．０Ｌ噴霧しながら、流動させつつ、上記した混合物（活性炭を含む組成物）を２５６０ｇ分が全量使用されるようにコーティング（厚み７６０μｍ）に供した（潜熱蓄熱材：活性炭：有機バインダー＝２５０：２３１７：２４２（質量比）である）。その後、１１５℃で３時間以上乾燥させ、成型物の含水率を５質量％未満とし、平均粒子径を２．０～２．４ｍｍに調整し、実施例８の潜熱蓄熱材一体型活性炭を得た。 Next, using the latent heat storage material obtained in Example 3 as a core, 250 g was charged into a granulator (manufactured in-house), and 1.5 to 2.0 L of 0.01 mass% PVA solution water was sprayed while spraying. While flowing, the above mixture (composition containing activated charcoal) was applied to a coating (thickness 760 μm) so that the entire amount of 2560 g was used (latent heat storage material: activated charcoal: organic binder = 250: 2317: 242 (mass ratio). ). Then, it was dried at 115 ° C. for 3 hours or more, the water content of the molded product was set to less than 5% by mass, the average particle size was adjusted to 2.0 to 2.4 mm, and the latent heat storage material integrated activated carbon of Example 8 was obtained. rice field.
　実施例９
　潜熱蓄熱材として実施例４で得られた潜熱蓄熱材を使用し、活性炭混合物（活性炭を含む組成物）を１１８７ｇ分が全量使用されるようにコーティング（厚み６４０μｍ）に供した（潜熱蓄熱材：活性炭：有機バインダー＝２５０：１０７４：１１２（質量比）である）他は実施例８と同様に、実施例９の潜熱蓄熱材一体型活性炭を得た。 Example 9
The latent heat storage material obtained in Example 4 was used as the latent heat storage material, and a mixture of activated charcoal (composition containing active charcoal) was applied to a coating (thickness 640 μm) so that the entire amount of 1187 g was used (latent heat storage material: Activated charcoal: organic binder = 250: 1074: 112 (mass ratio)) In the same manner as in Example 8, a latent heat storage material-integrated activated charcoal of Example 9 was obtained.
　実施例１０
　潜熱蓄熱材として実施例５で得られた潜熱蓄熱材を使用し、活性炭混合物（活性炭を含む組成物）を６２０ｇ分が全量使用されるようにコーティング（厚み５３０μｍ）に供した（潜熱蓄熱材：活性炭：有機バインダー＝２５０：５６２：５９（質量比）である）他は実施例８と同様に、実施例１０の潜熱蓄熱材一体型活性炭を得た。 Example 10
The latent heat storage material obtained in Example 5 was used as the latent heat storage material, and a mixture of activated charcoal (composition containing active charcoal) was applied to a coating (thickness 530 μm) so that the entire amount of 620 g was used (latent heat storage material: Activated charcoal: organic binder = 250: 562: 59 (mass ratio)) In the same manner as in Example 8, a latent heat storage material-integrated activated charcoal of Example 10 was obtained.
　試験例２
　燃料蒸散ガス吸着性能を表すブタンアクティビティ（ＢＡ）：ＡＳＴＭ－Ｄ５２２８に準拠して測定した（以下、ＢＡと略記する）。供する潜熱蓄熱材一体型球状活性炭は平均粒子径が２．３６ｍｍ以上２．８０ｍｍ未満となるものに限定した。結果を表２及び３に示す。 Test Example 2
Butane activity (BA) representing fuel evaporation gas adsorption performance: Measured in accordance with ASTM-D5228 (hereinafter abbreviated as BA). The spherical activated carbon integrated with the latent heat storage material to be provided was limited to those having an average particle size of 2.36 mm or more and less than 2.80 mm. The results are shown in Tables 2 and 3.
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
　実施例８～１０から、潜熱蓄熱材一体型球状活性炭に適した、潜熱蓄熱材の直径サイズと配合率を確認することができる。すなわち、潜熱蓄熱材の直径が、適度な範囲にあればＢＡ値が４２％以上となり、これは高い吸脱着能が得られることも意味する。 From Examples 8 to 10, it is possible to confirm the diameter size and compounding ratio of the latent heat storage material suitable for the latent heat storage material integrated spherical activated carbon. That is, if the diameter of the latent heat storage material is within an appropriate range, the BA value becomes 42% or more, which also means that a high adsorption / desorption ability can be obtained.
　実施例１１
　潜熱蓄熱材として実施例４で得られた潜熱蓄熱材を核として使用し、活性炭混合物（活性炭を含む組成物）を２８５４ｇ分が全量使用されるようにコーティング（厚み１０００μｍ）に供した（潜熱蓄熱材：活性炭：有機バインダー＝２５０：２５８３：２７０（質量比）である）他は実施例８と同様に、実施例１１の潜熱蓄熱材一体型活性炭を得た。この際、３．５（目開き５．６ｍｍ）～１０Ｍｅｓｈ（目開き１．７ｍｍ）（ＪＩＳ規格）の篩を用いて篩別し、目標粒度より大きい区分と１０Ｍｅｓｈよりも細かい区分を除いて任意の潜熱蓄熱材一体型球状活性炭を得た。 Example 11
The latent heat storage material obtained in Example 4 was used as the core as the latent heat storage material, and the activated charcoal mixture (composition containing active charcoal) was applied to a coating (thickness 1000 μm) so that the entire amount of 2854 g was used (latent heat storage material). Material: Activated charcoal: Organic binder = 250: 2583: 270 (mass ratio)) Other than that, the latent heat storage material integrated activated charcoal of Example 11 was obtained in the same manner as in Example 8. At this time, sieving is performed using a sieve having a size of 3.5 (opening 5.6 mm) to 10Mesh (opening 1.7 mm) (JIS standard), and is arbitrary except for a section larger than the target particle size and a section finer than 10Mesh. Spherical activated carbon integrated with latent heat storage material was obtained.
　実施例１２
　潜熱蓄熱材として実施例４で得られた潜熱蓄熱材を核として使用し、活性炭混合物（活性炭を含む組成物）を２０００ｇ分が全量使用されるようにコーティング（厚み８４０μｍ）に供した（潜熱蓄熱材：活性炭：有機バインダー＝２５０：１８１１：１８９（質量比）である）他は実施例１１と同様に、実施例１２の潜熱蓄熱材一体型活性炭を得た。 Example 12
The latent heat storage material obtained in Example 4 was used as the core as the latent heat storage material, and an activated charcoal mixture (composition containing active charcoal) was applied to a coating (thickness 840 μm) so that the entire amount of 2000 g was used (latent heat storage material). Material: Activated charcoal: Organic binder = 250: 1811: 189 (mass ratio)) Other than that, the latent heat storage material integrated activated charcoal of Example 12 was obtained in the same manner as in Example 11.
　実施例１３
　潜熱蓄熱材として実施例４で得られた潜熱蓄熱材を核として使用し、活性炭混合物（活性炭を含む組成物）を１３４７ｇ分が全量使用されるようにコーティング（厚み６８０μｍ）に供した（潜熱蓄熱材：活性炭：有機バインダー＝２５０：１２２０：１２７（質量比）である）他は実施例１１と同様に、実施例１２の潜熱蓄熱材一体型活性炭を得た。 Example 13
The latent heat storage material obtained in Example 4 was used as the core as the latent heat storage material, and the activated charcoal mixture (composition containing active charcoal) was applied to a coating (thickness 680 μm) so that the entire amount of 1347 g was used (latent heat storage material). Material: Activated charcoal: Organic binder = 250: 1220: 127 (mass ratio)) In the same manner as in Example 11, a latent heat storage material-integrated activated charcoal of Example 12 was obtained.
　実施例１４
　潜熱蓄熱材として実施例５で得られた潜熱蓄熱材を核として使用し、活性炭混合物（活性炭を含む組成物）を６９１ｇ分が全量使用されるようにコーティング（厚み５６０μｍ）に供した（潜熱蓄熱材：活性炭：有機バインダー＝２５０：６２５：６５（質量比）である）他は実施例１１と同様に、実施例１２の潜熱蓄熱材一体型活性炭を得た。 Example 14
The latent heat storage material obtained in Example 5 was used as the core as the latent heat storage material, and an activated charcoal mixture (composition containing active charcoal) was applied to a coating (thickness 560 μm) so that 691 g of the mixture was used in its entirety (latent heat storage material). Material: Activated charcoal: Organic binder = 250: 625: 65 (mass ratio)) Other than that, the latent heat storage material integrated activated charcoal of Example 12 was obtained in the same manner as in Example 11.
　参考例１
　潜熱蓄熱材を用いない既存の活性炭（ＩｎｇｅｖｉｔｙＣｏｒｐｏｒａｔｉｏｎ製のＢＡＸ１１００）を使用した。 Reference example 1
An existing activated carbon (BAX1100 manufactured by Industry Corporation) that does not use a latent heat storage material was used.
　参考例２
　潜熱蓄熱材を用いない既存の活性炭（ＩｎｇｅｖｉｔｙＣｏｒｐｏｒａｔｉｏｎ製のＢＡＸ１７００）を使用した。 Reference example 2
An existing activated carbon (BAX1700 manufactured by Industry Corporation) that does not use a latent heat storage material was used.
　試験例３
　キャニスターケースＬ／Ｄ＝３．０を用い、潜熱蓄熱材一体型活性炭又は活性炭を１０００ｍＬ充填させた。給油条件（ＥＰＡで規定されるＯＲＶＲ試験条件）として、タンク内の残存液体ガソリン温度を２６．８℃とし、給油ガソリン温度を１９．２℃とし、ガソリン停止条件を３０００ｐｐｍ破過とした。潜熱蓄熱材一体型活性炭又は活性炭の前処理としてガソリン燃料を用いて６回吸脱着を繰り返した。Ｌ／Ｄは、活性炭層の中心軸方向の長さＬ［ｍｍ］÷平均直径Ｄ［ｍｍ］から求めた値である。結果は、参考例１を基準（１００）とした相対値として、表３に示す。 Test Example 3
Using a canister case L / D = 3.0, 1000 mL of latent heat storage material integrated activated carbon or activated carbon was filled. As the refueling conditions (ORVR test conditions specified by the EPA), the residual liquid gasoline temperature in the tank was set to 26.8 ° C, the refueling gasoline temperature was set to 19.2 ° C, and the gasoline stop condition was set to 3000 ppm breakthrough. As a pretreatment of the latent heat storage material-integrated activated carbon or activated carbon, gasoline fuel was used to repeat absorption and desorption 6 times. L / D is a value obtained from the length L [mm] ÷ average diameter D [mm] of the activated carbon layer in the central axis direction. The results are shown in Table 3 as relative values based on Reference Example 1 (100).
　試験例４
　ＡＳＴＭ－Ｄ５２２８を参考にしてＡＳＴＭ硬さを測定した。結果を表３に示す。 Test Example 4
The ASTM hardness was measured with reference to ASTM-D5228. The results are shown in Table 3.
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000003
　実施例１１～１４と参考例１及び２とを比較することで、潜熱蓄熱材一体型活性炭を使用することで、潜熱蓄熱材を用いない既存の活性炭（ＩｎｇｅｖｉｔｙＣｏｒｐｏｒａｔｉｏｎ製のＢＡＸ１１００）と比較して、ＧＷＣが著しく向上することが分かる（相対値１７２以上）。 By comparing Examples 11 to 14 with Reference Examples 1 and 2, by using the latent heat storage material integrated activated carbon, it is compared with the existing activated carbon (BAX1100 manufactured by Ingevity Corporation) that does not use the latent heat storage material. It can be seen that the GWC is significantly improved (relative value 172 or more).
　製造例１
　活性炭としては、ＪＩＳ　Ｋ　１４７４（２０１４）に準拠して測定した水懸濁液のｐＨが４．１９である活性炭を使用した。この活性炭と、有機バインダーと水とを混合し、押出し機（（株）ダルトン製のディスクペレッターＦ５型）を用いて孔径２．２ｍｍ、厚さ１５ｍｍのダイスで成形し、マルメライザー（ダルトン、Ｑ－４００Ｔ）にて細粒化を行うことで、蓄熱材一体型活性炭の活性炭含有層と同様の材料構成の成型物を得た。得られた成型物のｐＨは、ＪＩＳ　Ｋ　１４７４（２０１４）に準拠して測定した水懸濁液のｐＨが４．９７であった。ここで得られる成型物と硬さと蓄熱材一体型活性炭の硬さには正の相関がある。なお、有機バインダーとしては、カルボキシメチルセルロースナトリウム塩（日本製紙（株）製のＦ３０ＭＣ）、エポクロスＷＳ－７００（（株）日本触媒製のオキサゾリン基含有水溶性ポリマー）、ＡＤＥＫＡレジン（（株）ＡＤＥＫＡ製の水性エポキシ樹脂ＥＭ－０１８０）を選定し、固形分率で活性炭１００質量部に対してそれぞれ６．８質量部、１．２質量部、１．９質量部の計９．９質量部、水は活性炭１００質量部に対して２２０．０質量部を加えた。 Manufacturing example 1
As the activated carbon, activated carbon having a pH of 4.19 in an aqueous suspension measured according to JIS K 1474 (2014) was used. This activated carbon, an organic binder, and water are mixed and molded with a die having a hole diameter of 2.2 mm and a thickness of 15 mm using an extruder (disc pelleter F5 type manufactured by Dalton Co., Ltd.), and a malmerizer (Dalton, By finely granulating with Q-400T), a molded product having the same material composition as the activated carbon-containing layer of the heat storage material-integrated activated carbon was obtained. The pH of the obtained molded product was 4.97, which was the pH of the aqueous suspension measured according to JIS K 1474 (2014). There is a positive correlation between the hardness of the molded product obtained here and the hardness of the heat storage material integrated activated carbon. Examples of the organic binder include carboxymethyl cellulose sodium salt (F30MC manufactured by Nippon Paper Co., Ltd.), Epocross WS-700 (oxazoline group-containing water-soluble polymer manufactured by Nippon Catalyst Co., Ltd.), and ADEKA Resin (manufactured by ADEKA Corporation). Aqueous epoxy resin EM-0180) was selected, and the solid content was 6.8 parts by mass, 1.2 parts by mass, and 1.9 parts by mass, for a total of 9.9 parts by mass and water, respectively, with respect to 100 parts by mass of activated carbon. Added 220.0 parts by mass with respect to 100 parts by mass of activated charcoal.
　製造例２
　ＪＩＳ　Ｋ　１４７４（２０１４）に準拠して測定した水懸濁液のｐＨが４．５０である活性炭を用いる以外は、製造例１と同様の方法で、ＪＩＳ　Ｋ　１４７４（２０１４）に準拠して測定した水懸濁液のｐＨが５．８７の成型物を得た。 Manufacturing example 2
Measured in accordance with JIS K 1474 (2014) Measured in accordance with JIS K 1474 (2014) in the same manner as in Production Example 1 except that activated carbon having a pH of 4.50 in the aqueous suspension is used. A molded product having a pH of 5.87 was obtained.
　製造例３
　ＪＩＳ　Ｋ　１４７４（２０１４）に準拠して測定した水懸濁液のｐＨが７．３５である活性炭を用いる以外は、製造例１と同様の方法で、ＪＩＳ　Ｋ　１４７４（２０１４）に準拠して測定した水懸濁液のｐＨが６．５８の成型物を得た。 Manufacturing example 3
Measured in accordance with JIS K 1474 (2014) Measured in accordance with JIS K 1474 (2014) in the same manner as in Production Example 1 except that activated carbon having a pH of 7.35 in the aqueous suspension is used. A molded product having a pH of 6.58 was obtained.
　製造例４
　ＪＩＳ　Ｋ　１４７４（２０１４）に準拠して測定した水懸濁液のｐＨが９．５４である活性炭を用いる以外は、製造例１と同様の方法で、ＪＩＳ　Ｋ　１４７４（２０１４）に準拠して測定した水懸濁液のｐＨが９．１３の成型物を得た。 Manufacturing example 4
Measured in accordance with JIS K 1474 (2014) Measured in accordance with JIS K 1474 (2014) in the same manner as in Production Example 1 except that activated carbon having a pH of 9.54 is used for the aqueous suspension. A molded product having a pH of 9.13 was obtained.
　製造例５
　水酸化ナトリウム５０gを蒸留水２５０gに溶かし、活性炭１００ｇを加え、１２０℃で３時間乾燥させることで、ＪＩＳ　Ｋ　１４７４（２０１４）に準拠して測定した水懸濁液のｐＨが１１．２７である活性炭を作製した。この活性炭と、有機バインダーと水とを混合し、押出し機（（株）ダルトン製のディスクペレッターＦ５型）を用いて孔径２．２ｍｍ、厚さ１５のダイスで成形し、マルメライザー（ダルトン、Ｑ－４００Ｔ）にて細粒化を行うことで、蓄熱材一体型活性炭の活性炭含有層と同様の材料構成の成型物を得た。得られた成型物のｐＨは、ＪＩＳ　Ｋ　１４７４（２０１４）に準拠して測定した水懸濁液のｐＨが１０．４３であった。ここで得られる成型物と硬さと蓄熱材一体型活性炭の硬さには正の相関がある。なお、有機バインダーとしては、カルボキシメチルセルロースナトリウム塩（日本製紙（株）製のＦ３０ＭＣ）、エポクロスＷＳ－７００（（株）日本触媒製のオキサゾリン基含有水溶性ポリマー）、ＡＤＥＫＡレジン（（株）ＡＤＥＫＡ製の水性エポキシ樹脂ＥＭ－０１８０）を選定し、固形分率で活性炭１００質量部に対してそれぞれ６．８質量部、１．２質量部、１．９質量部の計９．９質量部、水は活性炭１００質量部に対して２１５．０質量部を加えた。 Production example 5
By dissolving 50 g of sodium hydroxide in 250 g of distilled water, adding 100 g of activated carbon, and drying at 120 ° C. for 3 hours, the pH of the aqueous suspension measured in accordance with JIS K 1474 (2014) is 11.27. Activated carbon was prepared. This activated carbon, an organic binder, and water are mixed and molded with a die having a hole diameter of 2.2 mm and a thickness of 15 using an extruder (disc pelleter F5 type manufactured by Dalton Co., Ltd.), and a malmerizer (Dalton, By finely granulating with Q-400T), a molded product having the same material composition as the activated carbon-containing layer of the heat storage material-integrated activated carbon was obtained. The pH of the obtained molded product was 10.43, which was the pH of the aqueous suspension measured according to JIS K 1474 (2014). There is a positive correlation between the hardness of the molded product obtained here and the hardness of the heat storage material integrated activated carbon. Examples of the organic binder include carboxymethyl cellulose sodium salt (F30MC manufactured by Nippon Paper Co., Ltd.), Epocross WS-700 (oxazoline group-containing water-soluble polymer manufactured by Nippon Catalyst Co., Ltd.), and ADEKA Resin (manufactured by ADEKA Corporation). Aqueous epoxy resin EM-0180) was selected, and the solid content was 6.8 parts by mass, 1.2 parts by mass, and 1.9 parts by mass, for a total of 9.9 parts by mass and water with respect to 100 parts by mass of activated carbon. Added 215.0 parts by mass with respect to 100 parts by mass of activated charcoal.
　比較製造例１
　ＪＩＳ　Ｋ　１４７４（２０１４）に準拠して測定した水懸濁液のｐＨが２．９２である活性炭を用いる以外は、製造例１と同様の方法で、ＪＩＳ　Ｋ　１４７４（２０１４）に準拠して測定した水懸濁液のｐＨが２．８８の成型物を得た。 Comparative manufacturing example 1
Measured in accordance with JIS K 1474 (2014) Measured in accordance with JIS K 1474 (2014) in the same manner as in Production Example 1 except that activated charcoal having a pH of 2.92 in the aqueous suspension is used. A molded product having a pH of 2.88 was obtained.
　試験例５
　ＡＳＴＭ－Ｄ５２２８を参考にしてＡＳＴＭ硬さを測定した。結果を表４に示す。なお、表４には、各成型物のｐＨが４．５以上である場合をＡ、４．５未満である場合をＢと表記した。 Test Example 5
The ASTM hardness was measured with reference to ASTM-D5228. The results are shown in Table 4. In Table 4, the case where the pH of each molded product was 4.5 or more was designated as A, and the case where the pH was less than 4.5 was designated as B.
Figure JPOXMLDOC01-appb-T000004
Figure JPOXMLDOC01-appb-T000004
　製造例１～５及び比較製造例１を比較することにより、元炭のｐＨは３以上であればｐＨに限らず使用可能であり、蓄熱材一体型活性炭の活性炭含有層のｐＨはＡ（４．５以上）が好ましいことが理解できる。 By comparing Production Examples 1 to 5 and Comparative Production Example 1, if the pH of the original coal is 3 or more, it can be used regardless of the pH, and the pH of the activated carbon-containing layer of the heat storage material integrated activated carbon is A (4). It can be understood that (5.5 or more) is preferable.

Claims (15)

  1. 温度に応じて潜熱の吸収及び放出を生じる相変化物質を封入したマイクロカプセルを有する潜熱蓄熱材と、活性炭とを含有する潜熱蓄熱材一体型活性炭であって、
    前記潜熱蓄熱材は、前記マイクロカプセルの表面が熱硬化性有機バインダーＡを含む有機バインダー含有層で被覆されており、且つ、
    前記潜熱蓄熱材の表面が活性炭を含む活性炭含有層で被覆されている、潜熱蓄熱材一体型活性炭。     A latent heat storage material integrated activated carbon containing microcapsules containing a phase-changing substance that absorbs and releases latent heat depending on the temperature and activated carbon.
    In the latent heat storage material, the surface of the microcapsules is coated with an organic binder-containing layer containing a thermosetting organic binder A, and the latent heat storage material is coated with an organic binder-containing layer.
    An activated carbon integrated with a latent heat storage material in which the surface of the latent heat storage material is coated with an activated carbon-containing layer containing activated carbon.
  2. 前記マイクロカプセルの平均粒子径が０．１～５００μｍである、請求項１に記載の潜熱蓄熱材一体型活性炭。 The activated carbon integrated with a latent heat storage material according to claim 1, wherein the microcapsules have an average particle size of 0.1 to 500 μm.
  3. 前記活性炭の平均粒子径が１μｍ～１０ｍｍである、請求項１又は２に記載の潜熱蓄熱材一体型活性炭。 The activated carbon integrated with a latent heat storage material according to claim 1 or 2, wherein the activated carbon has an average particle size of 1 μm to 10 mm.
  4. 前記活性炭含有層が、さらに、有機バインダーＢを含有する、請求項１～３のいずれか１項に記載の潜熱蓄熱材一体型活性炭。 The activated carbon integrated with a latent heat storage material according to any one of claims 1 to 3, wherein the activated carbon-containing layer further contains an organic binder B.
  5. ＪＩＳ　Ｋ　１４７４（２０１４）に準拠して測定した、前記活性炭含有層の水懸濁液のｐＨが４．５以上である、項１～４のいずれか１項に記載の潜熱蓄熱材一体型活性炭。 Item 2. The latent heat storage material integrated activated carbon according to any one of Items 1 to 4, wherein the pH of the aqueous suspension of the activated carbon-containing layer measured in accordance with JIS K 1474 (2014) is 4.5 or more. ..
  6. 前記潜熱蓄熱材の平均断面直径が０．７５～１．８０ｍｍである、請求項１～５のいずれか１項に記載の潜熱蓄熱材一体型活性炭。 The activated carbon integrated with a latent heat storage material according to any one of claims 1 to 5, wherein the latent heat storage material has an average cross-sectional diameter of 0.75 to 1.80 mm.
  7. 前記潜熱蓄熱材の含有量が、前記潜熱蓄熱材一体型活性炭の総量を１００質量％として、７～３０質量％である、請求項１～６のいずれか１項に記載の潜熱蓄熱材一体型活性炭。 The latent heat storage material integrated type according to any one of claims 1 to 6, wherein the content of the latent heat storage material is 7 to 30% by mass, where the total amount of the latent heat storage material integrated activated carbon is 100% by mass. Activated carbon.
  8. 熱量が１０～１００Ｊ／ｇである、請求項１～７のいずれか１項に記載の潜熱蓄熱材一体型活性炭。 The activated carbon integrated with a latent heat storage material according to any one of claims 1 to 7, which has a calorific value of 10 to 100 J / g.
  9. ＡＳＴＭ硬さが４５％以上である、請求項１～８のいずれか１項に記載の潜熱蓄熱材一体型活性炭。 The activated carbon integrated with a latent heat storage material according to any one of claims 1 to 8, which has an ASTM hardness of 45% or more.
  10. 請求項１～９のいずれか１項に記載の潜熱蓄熱材一体型活性炭の製造方法であって、
    （１）前記マイクロカプセルと前記熱硬化性有機バインダーＡとを混合する工程
    （２）工程（１）で得られたマイクロカプセル組成物を前記熱硬化性有機バインダーＡで被覆し、熱処理して前記潜熱蓄熱材を得る工程、
    （３）工程（２）で得られた潜熱蓄熱材と、前記活性炭を含む組成物とを混合して造粒する工程
    を備える、製造方法。     The method for producing an activated carbon integrated with a latent heat storage material according to any one of claims 1 to 9.
    (1) Step of mixing the microcapsules and the thermosetting organic binder A (2) The microcapsule composition obtained in step (1) is coated with the thermosetting organic binder A and heat-treated to obtain the above. The process of obtaining latent heat storage material,
    (3) A production method comprising a step of mixing and granulating the latent heat storage material obtained in the step (2) and the composition containing the activated carbon.
  11. 前記工程（１）が、前記マイクロカプセルと前記熱硬化性有機バインダーＡとを混合後に押出造粒し、次いで整粒する工程である、請求項１０に記載の製造方法。 The production method according to claim 10, wherein the step (1) is a step of mixing the microcapsules and the thermosetting organic binder A, then extruding and granulating, and then sizing.
  12. 前記工程（３）において、前記活性炭を含む組成物が、さらに、前記有機バインダーＢを含有する、請求項１０又は１１に記載の製造方法。 The production method according to claim 10 or 11, wherein in the step (3), the composition containing the activated carbon further contains the organic binder B.
  13. 前記工程（３）において、前記活性炭を含む組成物が、さらに、ｐＨ調整剤を含有する、請求項１０～１２のいずれか１項に記載の製造方法。 The production method according to any one of claims 10 to 12, wherein in the step (3), the composition containing the activated carbon further contains a pH adjuster.
  14. 請求項１～９のいずれか１項に記載の潜熱蓄熱材一体型活性炭を含有する、キャニスター。 A canister containing the latent heat storage material integrated activated carbon according to any one of claims 1 to 9.
  15. 請求項１～９のいずれか１項に記載の潜熱蓄熱材一体型活性炭を含有する、密閉式ガソリンタンクと連結されている自動車用キャニスター。 An automobile canister connected to a closed gasoline tank containing the latent heat storage material integrated activated carbon according to any one of claims 1 to 9.
PCT/JP2021/013531 2020-04-13 2021-03-30 Latent heat storage material-integrated active carbon and production method thereof WO2021210386A1 (en)

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